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[ CAS No. 4422-95-1 ] {[proInfo.proName]}

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Chemical Structure| 4422-95-1
Chemical Structure| 4422-95-1
Structure of 4422-95-1 * Storage: {[proInfo.prStorage]}
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Product Details of [ 4422-95-1 ]

CAS No. :4422-95-1 MDL No. :MFCD00000679
Formula : C9H3Cl3O3 Boiling Point : -
Linear Structure Formula :- InChI Key :UWCPYKQBIPYOLX-UHFFFAOYSA-N
M.W : 265.48 Pubchem ID :78138
Synonyms :

Calculated chemistry of [ 4422-95-1 ]

Physicochemical Properties

Num. heavy atoms : 15
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.0
Num. rotatable bonds : 3
Num. H-bond acceptors : 3.0
Num. H-bond donors : 0.0
Molar Refractivity : 56.99
TPSA : 51.21 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.47 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.68
Log Po/w (XLOGP3) : 3.45
Log Po/w (WLOGP) : 2.82
Log Po/w (MLOGP) : 1.8
Log Po/w (SILICOS-IT) : 3.43
Consensus Log Po/w : 2.64

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 0.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -3.76
Solubility : 0.0464 mg/ml ; 0.000175 mol/l
Class : Soluble
Log S (Ali) : -4.21
Solubility : 0.0165 mg/ml ; 0.0000621 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -4.09
Solubility : 0.0214 mg/ml ; 0.0000807 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 1.0 alert
Leadlikeness : 0.0
Synthetic accessibility : 1.36

Safety of [ 4422-95-1 ]

Signal Word:Danger Class:8
Precautionary Statements:P260-P280-P303+P361+P353-P304+P340+P310-P305+P351+P338 UN#:3261
Hazard Statements:H302-H314 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 4422-95-1 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 4422-95-1 ]

[ 4422-95-1 ] Synthesis Path-Downstream   1~85

  • 1
  • [ 554-95-0 ]
  • [ 4422-95-1 ]
YieldReaction ConditionsOperation in experiment
100% With thionyl chloride In N,N-dimethyl-formamide for 8h; Heating;
100% With thionyl chloride In N,N-dimethyl-formamide for 3h; Heating;
100% With thionyl chloride; N,N-dimethyl-formamide for 3h; Heating / reflux; 1,3,5-benzenetricarboxylic acid (6.0 g, 28.7 mmol) was placed in a flask together with SOCl2 (12 ml) and a drop of DMF. The suspension was refluxed for 3 h, resulting in a clear solution. The remaining SOCl2 was evaporated in vacuo, yielding a pale yellow oil which formed crystals upon standing in the cooling cell (7.7 g, 28.7 mmol, 100%).
100% With thionyl chloride; N,N-dimethyl-formamide Reflux; Inert atmosphere;
100% With thionyl chloride at 80℃; for 4h;
100% With thionyl chloride for 4h; Heating / reflux; Preparation of 3,5-Bis [(λ/-nitroso methylamino)carbamoyl benzoic acidTrimesic acid (2Og, 95 mmol) was suspended in thionyl chloride (60 mL) and N, N- dimethylformamide (0.369 mL). The mixture was heated at reflux for 4 hours till gas evolution had ceased. The reaction mixture was concentrated in vacuo then dissolved in dichloromethane (2x50 mL) and the solution concentrated in vacuo. Trimesoyl chloride was isolated as a yellow solid (25g, 100%).
98% With thionyl chloride In N,N-dimethyl-formamide for 4h; Reflux;
98.5% With thionyl chloride In tetrahydrofuran at 800℃; for 5h; 1.1-1.2; 2.1-2.2 Example 2 A process for preparing trimesoyl chloride, which comprises the steps of:(1) using trimesic acid and thionyl chloride as raw materials, adding a mixed catalyst, refluxing in tetrahydrofuran, the reaction temperature is 800 ° C, the reaction time is 5 h, and the volume ratio of tetrahydrofuran to thionyl chloride is 5:1. The molar ratio of trimesic acid to thionyl chloride is 1:3, and the amount of mixed catalyst is 2% of the mass of trimesic acid.The mixed catalyst is N,N-dimethylformamide, octadecyltrimethylammonium bromide and methoxymethyltriphenylphosphonium chloride mixed at a mass ratio of 2:1:1;(2) After completion of the reaction, the tetrahydrofuran and thionyl chloride are distilled off under reduced pressure, the distillation pressure is 600 mmHg, the temperature is 80 ° C, and then vacuum distillation is carried out to obtain trimesoyl chloride, vacuum distillation vacuum is 740 mmHg, and 76 ° C fraction is collected. .The synthesized trimesoyl chloride content was 99.5%, and the reaction yield was 98.5%.
97.5% With Benzotrichlorid; zinc oxide at 140℃; for 4h; 6 To the 2 L four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 600 g (2.86 mol) of trimesic acid having a sodium content of 8 ppm obtained in Example 2, 1776 g (9.09 mol) of trichloromethylbenzene, Zinc oxide 0.36 g (0.004 mol 1), and the reaction vessel was heated to 140 ° C to carry out the reaction. (Trichloromethyl) benzene remained at 1% or less after 4 hours. Thereafter, it was allowed to react for 13 hours, 62 g of benzoic acid (0.5 lmo 1) was added, and further reacted for 2 hours to obtain 2234 g of crude trimesoyl chloride. To this was added 56 g (0.004 mol) of hexamethylenetetramine, and distilled under reduced pressure (0.8 kPa · abs) to obtain 740 g of trimesoyl chloride (yield: 97.5%, purity: 99.7%).
95% With thionyl chloride; N,N-dimethyl-formamide for 18h; Heating;
93.2% With thionyl chloride; stearyl trimethyl ammonium bromide In N,N-dimethyl-formamide at 75℃; for 100h; 1-2 (1) using trimesic acid and thionyl chloride under the action of a mixed catalyst,The reaction, the molar ratio of trimesic acid to thionyl chloride is 1:8,The reaction temperature is 75 ° C, and the time is 100 hours;The mixed catalyst is N, N-dimethylformamide and octadecyltrimethylammonium bromide mixed in a mass ratio of 1:2, and the amount of the catalyst is 5% of the mass of the trimesic acid;(2) After completion of the reaction, it was cooled to a temperature of 15 ° C, and recrystallized from diethyl ether to give the benzene.The obtained product content was 99.0%, and the yield was 93.2%.
91% With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0 - 20℃; for 4h;
90% With thionyl chloride
90% With thionyl chloride; N,N-dimethyl-formamide for 2.5h; Heating;
76.4% With phosphorus(V) chloride at 200℃;
71% With pyridine; thionyl chloride for 336h; Heating;
With phosphorus(V) chloride
With phosphorus(V) chloride; trichlorophosphate
With thionyl chloride
With 1-methyl-pyrrolidin-2-one; thionyl chloride
With thionyl chloride
With pyridine; thionyl chloride
With oxalyl dichloride; N,N-dimethyl-formamide In toluene at 60℃; for 3h;
With thionyl chloride for 1h; Heating;
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane
With thionyl chloride; N,N-dimethyl-formamide for 6h; Heating;
With thionyl chloride; N,N-dimethyl-formamide Heating;
With pyridine; thionyl chloride at 75℃; for 14h;
With thionyl chloride In <i>N</i>-methyl-acetamide 1 EXAMPLE 1 EXAMPLE 1 Preparation of component A (formula 1 of the above series of formulae) 42.0 g of trimesic acid are heated for 5 hours to 80° C. with 144.0 ml of thionyl chloride in the presence of a catalytic quantity (3 ml) of dimethylformamide, then the excess thionyl chloride is distilled off, and the trimesic acid trichloride thus formed is dissolved in 500 ml of dioxane.
With thionyl chloride; N,N-dimethyl-formamide at 20℃; Reflux;
With thionyl chloride for 12h; Reflux;
With thionyl chloride for 4h; Reflux;
With thionyl chloride at 70℃; for 24h;
With thionyl chloride In tetrahydrofuran at 70℃; for 4h;
With thionyl chloride In N,N-dimethyl-formamide for 6h; Reflux;
With thionyl chloride
With thionyl chloride In N,N-dimethyl-formamide
With thionyl chloride; N,N-dimethyl acetamide at 80℃; for 10h;
With thionyl chloride for 4h; Reflux; General procedure for the synthesisof target compounds 10a-d. General procedure: 1,3,5-benzenetricarboxylic acid (0.26 g, 1.2mmol) in 6 ml of was heated under reflux for 4 h. The excess ofthionyl chloride was removed by vacuum distillation and 20 mL of pyridine and5-(2,4-acetoxyphenyl)tetrazole (2.0 g, 4mmol) was added. The mixture was heated under reflux for more 24 h. Aftercooling, the solution was poured into ice/water (250 mL) and the precipitatewas filtered off and washed with water. The purification was by column chromatographywith dichloromethane/ethyl acetate (95:5) as the eluent, resulting in 1.7 g ofcompound 10a.
With thionyl chloride; N,N-dimethyl-formamide In tetrahydrofuran Reflux;
With thionyl chloride In N,N-dimethyl-formamide at 55 - 60℃; for 4h;
With thionyl chloride In N,N-dimethyl-formamide for 3h; Reflux; 1 The 14.4mmol (3.0g) 1,3,5- benzenetricarboxylic acid was added to a round bottom flask equipped with a magnetic child then added 5mL of SOCl2 Further drop of DMF (N, N- dimethylformamide), in CJ78-1 magnetic stirrer under reflux until no mist is released, reflux was continued for 3 hours so that the reaction was complete, to SHZ-D (III ) circulating water pumps vacuum distillation to remove excess SOCl2 And cooled to give a pale yellow acid chloride.
With thionyl chloride In tetrahydrofuran at 80℃; for 2h; Schlenk technique; Inert atmosphere;
With pyridine; thionyl chloride for 24h; Reflux; Inert atmosphere;
With phosphorus(V) chloride In toluene Inert atmosphere; Reflux;
With thionyl chloride; N,N-dimethyl-formamide In dichloromethane for 3h; Reflux; 2 Method A - General procedure for the preparation of M47, M49, M50, M64 and M65: General procedure: A mixture of 1 ,3,5-benzenetricarboxylic acid 8 (0.21 g, 1 mmol), SOCI2(2 mL, 28 mmol) and two drops of DMF was heated under reflux for 3 hours. After cooling to room temperature, the excess SOCb was removed in vacuo to give 1 ,3,5- benzenetricarboxylic chloride, which was used without further purification. To a mixture of amine 9 (3.3 mmol), and Et3N (1.4 mL, 10 mmol) in 10 mL CH2CI2at 0°C, 1 ,3,5- benzenetricarboxylic chloride in CH2CI2 was added slowly. The mixture was stirred at r.t. for 4 hours. The reaction mixture was washed with water, brine. The combined organic layers were dried over anhydrous Na2S04 and concentrated in vacuo. The crude residue was recrystalized from EtOH to afford pure product amide M47, M49, M50, M64 and M65.
With thionyl chloride Heating;
With thionyl chloride
Stage #1: benzene-1,3,5-tricarboxylic acid With oxalyl dichloride In dichloromethane at 0℃; for 0.166667h; Stage #2: With N,N-dimethyl-formamide In dichloromethane for 12h; Reflux;
With thionyl chloride; N,N-dimethyl-formamide Reflux;
With thionyl chloride; sulfuric acid for 0.85h; Inert atmosphere; Reflux; General Procedure of Chlorination General procedure: To a 50 mL round bottom flask with substrate 10.0 mmol, SOCl2 60 mmol (7.14 g), H2SO4 2 mmol (0.2 g) was added under reflux with a low-temperature condenser (with circulating coolant at -10 °C, and N2 was used as protective gas, TLC was used to track the reaction to the end. Excess SOCl2 was removed by atmospheric distillation to obtain crude acyl chloride.
With thionyl chloride for 2h; Reflux;
With phosphorus trichloride at 60℃; 3.3; 4.2 2) Preparation of trimesoyl chloride: 70 mol of trimesic acid and 210 mol of phosphorus trichloride were added dropwise to the reaction kettle, stirred and heated to 60° C., cooled to room temperature, and left to stand for layering to obtain trimesic acid chloride.
With thionyl chloride In N,N-dimethyl-formamide at 90℃; for 5h; 1.1 (1) Slowly add 1,3,5-benzenetricarboxylic acid (2.1g, 10mmol), thionyl chloride (6mL, 33mmol) and N,N'-dimethylformamide (0.1mL) to a 50mL round bottom flask. ), the reaction was heated at 90°C under reflux for 5h, until the 1,3,5-benzenetricarboxylic acid was completely reacted. After removing the excess thionyl chloride under vacuum, the crude product of 1,3,5-benzenetricarboxylic acid chloride can be obtained as a yellow oil, and the next step can be carried out directly without further treatment.
With thionyl chloride; N,N-dimethyl-formamide at 90℃; for 5h;
With thionyl chloride In N,N-dimethyl-formamide Reflux;
With oxalyl dichloride In dichloromethane; N,N-dimethyl-formamide at 0℃; for 1h;

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  • 2
  • [ 5666-55-7 ]
  • [ 4422-95-1 ]
  • [ 10365-94-3 ]
  • 5
  • [ 67-56-1 ]
  • [ 4422-95-1 ]
  • [ 2672-58-4 ]
YieldReaction ConditionsOperation in experiment
93% With trimethylamine In chloroform Heating;
64.5% With triethylamine for 2h; ice bath;
2.4 g With triethylamine In dichloromethane at 0℃; Inert atmosphere; General Procedure of Derivatization General procedure: To a 50 mL round bottom flask with Et3N 12 mmol (1.21 g), CH3OH 1.2 equimolar (The amount of CH3OH depends on the number of acyl chloride groups contained in the substrate, 0.38 g CH3OH per acyl chloride group), CH2Cl2 10mL was added at 0°C. The acyl chloride 10 mmol was dissolved in CH2Cl2 5 mL and slowly added dropwise to the round bottom flask under N2 atmosphere through a syringe, the reaction mixture was maintained at -0°C, after completion of the reaction monitored by TLC, removed excess solvent, washed the residue with water 20 mL to obtain the crude product. The crude product was further purified by silica gel column chromatography (200-300 mesh), and n-hexane and ethyl acetate were used as eluents.
  • 6
  • [ 100-02-7 ]
  • [ 4422-95-1 ]
  • [ 56173-27-4 ]
YieldReaction ConditionsOperation in experiment
92% With N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 20h; Inert atmosphere;
65% With triethylamine In acetonitrile Ambient temperature;
12% In N,N-dimethyl-formamide at 0 - 25℃; for 13h;
  • 7
  • [ 3147-55-5 ]
  • [ 4422-95-1 ]
  • [ 144181-06-6 ]
  • 8
  • [ 18655-50-0 ]
  • [ 4422-95-1 ]
  • Benzene-1,3,5-tricarboxylic acid tris-[3-(4-chloro-phenyl)-propyl]-amide} [ No CAS ]
  • 10
  • [ 4422-95-1 ]
  • [ 109-73-9 ]
  • N<SUP>1</SUP>,N<SUP>3</SUP>,N<SUP>5</SUP>-tri-n-butyltrimesoylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% With triethylamine In tetrahydrofuran
70% With sodium carbonate In 1,4-dioxane for 1h; Heating;
67% With pyridine; lithium chloride In 1-methyl-pyrrolidin-2-one at 0 - 60℃; Inert atmosphere;
40% With pyridine; lithium chloride In 1-methyl-pyrrolidin-2-one at 0 - 80℃; Inert atmosphere; 5 General procedure for preparation of 1 ,3,5-benzentricarboxylic acid trisamide derivatives N-methylpyrrolidone (NMP), pyridine, lithium chloride and the respective amine are put in a Schlenk flask under argon. 1 ,3,5-benzenetricarbonyl trichloride is slowly added at 00C under stirring and cooling with ice. Afterwards, the reaction mixture is stirred at 800C external oil bath temperature for 2h. After cooling, the reaction mass is dropped into the 5-fold amount of ice water and kept over night. After filtration, the crude material is dried under high vacuum and purified by recrystallisation from organic solvents. Example 5: 1 ,3,5-benzenetricarboxylic acid tris-(n-butylamide)(compound 105) batch: 8.00 g (0.030 mol) 1 ,3,5-benzentricarbonyl trichloride, 7.35 g (0.100 mol) n- butylamine, 250 ml NMP, 50 ml pyridine, 0,1 g LiCI purification: 2-fold crystallization from acetone yield: 4.40 g (0.012 mol / 40% of theory) rnp_: 239°C MS (70 eV): 375 (M+).
With pyridine In benzene Heating;
With triethylamine In tetrahydrofuran

  • 11
  • [ 4422-95-1 ]
  • [ 56-12-2 ]
  • [ 323202-30-8 ]
YieldReaction ConditionsOperation in experiment
91% Stage #1: 1,3,5-benzene tris(carbonyl chloride); 4-amino-n-butyric acid With sodium hydroxide In dichloromethane at 20℃; Ice bath; Stage #2: With hydrogenchloride In dichloromethane; water 9 Example 9 - Synthesis of benzene-l,3,5-tricarboxy-(N-ω-aminoacid-NHS ester) amide frameworksA solution of 1,3,5-benzenetricarbonyl chloride (1 gm, 3.8 mmole) in dichloromethane (DCM) (5 rnL) is added drop-wise to a vigorously stirring solution of an ω-aminoacid (3.1 equivalents) in IN NaOH (25 mL) in an ice bath. The ice bath is removed and stirring is continued for 4 hours at room temperature. 2N HCl (~15 mL) is added dropwise to approximately pH 2 and the resulting slurry is stirred for an additional 2 hours. The precipitate is filtered, washed with cold water (2x20 mL) and dried in air under vacuum and then in a 60 C oven overnight. The resulting white solid is used without further purification. Yield for each ω- aminoacid (4-aminobutyric acid: yield 1.6 gm, 91%; 6-aminocaproic acid: yield 1.9 gm, 92%)
With sodium hydroxide
  • 12
  • [ 4422-95-1 ]
  • [ 62-53-3 ]
  • [ 71764-61-9 ]
YieldReaction ConditionsOperation in experiment
100% With pyridine In dichloromethane at 20℃; for 1h;
90% Stage #1: 1,3,5-benzene tris(carbonyl chloride); aniline In pyridine; dichloromethane at 0℃; for 1h; Stage #2: In pyridine; dichloromethane at 0 - 20℃; for 4h;
83% In 5,5-dimethyl-1,3-cyclohexadiene at 30℃; for 0.583333h; Sonication; 9 synthesis of N1,N3,N5-triphenylbenzenetrimesicacid amide((I)9) Weigh 1.40 g of aniline in a 100mL round bottom flask, add 50 mL of xylene, the round bottom flask into the ultrasonic reactor, set the radiation power of 150W, the reaction temperature of 30 ° C, open the reactor, the reaction solution by adding 10mL A solution of 1.31 g of trimellitic acid chloride in xylene was dissolved. After the reaction for 35 min, the mixture was filtered and washed with 5 mL of 10 wt% sodium hydroxide solution three times to give a white solid 1.8 (^, yield 83%, 1 ^: 244.5 ~ 245.3. (: 11 ^ (11-1): 3143 (Aromatic ring CH), Η NMR (DMSO,400MHz): 10.09 (d, 3H), 3042 ((- 11), 1744 (-0 = 0), 1565 and 1483 (benzene ring skeleton vibration) (T, 4H, CH), 7.08 (s, 2H, CH), 6 · (t, 4H, CH), 8.29 (d, 3H, Ar-H) 90 (d, 3H, CH)
72% With TEA In dichloromethane 1.) ice bath, 2 h, 2.) r.t., 12 h;
55% With pyridine In dichloromethane at 20℃;
54% In tetrahydrofuran at 0 - 20℃; for 0.75h; Inert atmosphere;
With triethylamine In dichloromethane for 0.166667h;

  • 13
  • [ 462-08-8 ]
  • [ 4422-95-1 ]
  • [ 201036-79-5 ]
YieldReaction ConditionsOperation in experiment
85% With triethylamine In tetrahydrofuran at 0℃; Inert atmosphere; 2.2. Synthesis of 1 General procedure: The THF solution of 1,3,5-benzenetricarbonyl chloride (0.5310 g, 2 mmol) was added dropwise to the THF solution (25 mL) of 3-aminopyridine (0.5647 g, 6 mmol) and triethylamine (1.0119 g, 10 mmol) at 0 °C with continuous stirring under nitrogen atmosphere. The solution was stirred overnight. THF was distilled off and the solid product thus obtained was washed with water and recrystallized from MeOH. Yield: 85%. This product was crystallized from MeOH as described in the results and discussion and obtained the crystals of three forms.
79% With triethylamine In tetrahydrofuran
64.97% With triethylamine In tetrahydrofuran for 48h; Heating;
With triethylamine In tetrahydrofuran
With triethylamine In dichloromethane

  • 14
  • [ 4422-95-1 ]
  • [ 613-94-5 ]
  • N',N''',N'''''-tri(benzoyl)benzene-1,3,5-tricarboxylic acid trihydrazide [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With potassium carbonate In tetrahydrofuran; water
87.3% With pyridine In N,N-dimethyl acetamide at 70℃; for 4h; Inert atmosphere;
85% With pyridine In tetrahydrofuran at 0℃; for 1h; 4 A solution of benzoic hydrazide (0.76 g, 5.6 mmol), 1,3,5-benzenetricarbonyl trichloride (0.50 g, 1.8 mmol), and pyridine (0.5 ml) in THF (10 mL) was stirred at 0° C. for 1 hour. Then the reaction mixture was allowed to warm to room temperature slowly and stirred for another 0.5 hour. The supernatant liquid was decanted and the solid product was washed with water and hot methanol to give a white powder (0.8 g, yield 85%). 1H NMR (200 MHz, DMSO-d6): 10.9 (s, 3H); 10.7 (s, 3H); 8.7 (s, 3H); 7.9 (m, 6H); 7.5 (m, 9H) ppm; IR (KBr): 1657, 1602, 1264 cm-1.
  • 15
  • [ 4422-95-1 ]
  • [ 258331-10-1 ]
  • benzene-1,3,5-tricarboxylic acid tris-(2-<i>tert</i>-butoxycarbonylmethyl-phenyl) ester [ No CAS ]
  • 16
  • [ 4422-95-1 ]
  • [ 57704-54-8 ]
  • benzene-1,3,5-tricarboxylic acid tris-(3-<i>tert</i>-butoxycarbonyl-phenyl) ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃;
  • 17
  • [ 18364-47-1 ]
  • [ 4422-95-1 ]
  • N,N',N''-trimethyl-N,N',N''-tris(3-pyridyl)-1,3,5-benzene tricarboxamide [ No CAS ]
  • 18
  • [ 4422-95-1 ]
  • [ 100-01-6 ]
  • benzene-1,3,5-tricarboxylic acid tris[(4-nitrophenyl)amide] [ No CAS ]
YieldReaction ConditionsOperation in experiment
94.2% With triethylamine In dichloromethane for 2h; Cooling with ice; 4.1 Step 1. Preparation of intermediate A. To a 50 mL vessel was added 20 mL of a dichloromethane solution containing 1.24 g (9.0 mmol) of p-nitroaniline, 1.60 mL of triethylamine was added as an acid scavenger, 10 ml of a dichloromethane solution containing 0.50 g (1.90 mmol) of 1,3,5-benzenetricarboxylic acid chloride was slowly added dropwise with stirring under ice-cooling, reaction 2h, filtered to get a yellowish green solid, washed several times with ethanol solution and dried in vacuo to give 1.02 g of product in 94.2% yield.
93% With triethylamine In dichloromethane at 20℃; for 0.5h;
84% In acetonitrile at 85℃;
With pyridine

  • 19
  • [ 4422-95-1 ]
  • [ 170161-27-0 ]
  • C84H144N12O21 [ No CAS ]
  • 20
  • [ 4422-95-1 ]
  • [ 347165-20-2 ]
YieldReaction ConditionsOperation in experiment
With sodium azide In tetrahydrofuran; water for 1.5h; cooling;
With sodium azide In tetrahydrofuran; water at 0℃; for 2h;
Multi-step reaction with 3 steps 1: 84 percent / 0.5 h / Heating 2: hydrazine / methanol / 18 h / Heating 3: NaNO2; conc. HCl / H2O / 1 h / 10 °C
With sodium azide In tetrahydrofuran; water at 0℃; for 2h; benz-U-Phe (MdL038) To a cooled (0 °C) solution of NaN3 (1.75 g, 0.027 mol) in H2O (10 ml) was added a cooled (0 °C) solution of 1,3,5-benzenetricarbonyl trichloride MdL012 (1.0 g, 3.77 mmol) in THF (10 ml). The mixture was stirred for 2 hours at 0 °C resulting in the formation of 1,3,5-benzenetricarbonyl triazide as a white precipitate. This precipitate can easily be isolated by filtration, however, because of the explosivity of the dry solid this is strongly rejected. Thus, cold toluene (100 ml) was added to the mixture to take up the acyl azide. The toluene layer was separated and washed with H2O and brine and dried over MgSO4. Subsequently, the toluene solution was heated at 100 °C till gas evolution stopped, yielding in situ the corresponding triisocyanate. The solution was allowed to cool to room temperature and MdL063 (3.45 g, 12.44 mmol) in toluene (30 ml) was added. The mixture was stirred for one night at room temperature, after which the solvents were evaporated in vacuo yielding a sticky solid. Column chromatography using an eluent gradient (CH2Cl2/MeOH; 200/0→ 200/5) on silica gel yielded MdL038 slightly contaminated. A second column chromatography (CH2Cl2/MeOH; 200/10) on silica gel yielded MdL038 as a pure colorless sticky solid (0.76 g, 0.74 mmol, 20 %). 1H NMR (DMSO-d6): δ = 8.62 (s, 3H), 7.31-7.16 (m, 15H), 7.08 (s, 3H), 6.27 (d, 3H, 3J = 7.7 Hz), 4.44 (m, 3H), 3.99 (t, 6H, 3J = 6.4 Hz), 2.97 (m, 6H), 1.48 (s, 6H), 1.20 (s, 30H), 0.83 (t, 9H, 3J = 6.6 Hz); 13C NMR (DMSO-d6): δ = 172.40, 154.66, 140.65, 136.93, 129.34, 128.55, 126.89, 100.55, 64.76, 54.04, 37.66, 31.41, 28.79, 28.20, 25.50, 22.26, 14.13; C60H84N6O9: calcd. C 69.74, H 8.19, N 8.13; found: C 69.72, H 8.23, N 8.12.
With sodium azide In tetrahydrofuran; water for 2.08h; Cooling with ice; ; Compounds (6) and (7) were produced with reference to J. Am. Chem. Soc. 2002, 124, 14759-14769.315 mg (1.2 mmol) of 1,3,5-benzenetricarbonyl trichloride (compound (5)) was dissolved in 2 ml of tetrahydrofuran, and stirred on an ice bath. A solution of 772 mg (11.9 mmol) of sodium azide dissolved in 3 ml of water was dropwise added thereto, taking 5 minutes, and then stirred for 2 hours on an ice bath. An aqueous saturated sodium hydrogencarbonate solution was added thereto followed by extraction with toluene, and the organic layer was washed with an aqueous saturated sodium hydrogencarbonate solution and saturated saline water. Subsequently, this was dried with magnesium sulfate and concentrated until the solution amount could reach 10 ml or so, thereby giving a toluene solution of 1,3,5-benzenetricarbonyl triazide (compound (6)). The formation of the compound (6) was confirmed by IR. The solution was stirred at 90° C. for 2 hours to give a toluene solution of 1,3,5-benzenetricarbonyl triisocyanate (compound (7)). The formation of the compound (7) was confirmed by IR.
With sodium azide In water; 1,2-dichloro-ethane at 0 - 25℃;
With sodium azide In tetrahydrofuran; water at 0℃; for 2h;
With sodium azide In tetrahydrofuran; water for 2h; Cooling with ice; 2.2.1. Synthesis of compound tBu-1 To an aqueous solution (10 ml) of NaN3 (1.22 g, 19 mmol) wasadded dropwise a tetrahydrofuran (THF, 5 ml) solution of 1,3,5-benzenetricarbonyl trichloride (0.50 g, 1.9 mmol) while coolingwith an ice bath. The reaction suspension was stirred for another2 h and then poured into water (50 ml), extracted with toluene(50 ml 2). The combined organic layer was washed by saturatedNaHCO3 solution and brine, dried over anhydrous Na2SO4 and concentratedby evaporating until a volume of around 40 ml wasreached. The obtained toluene solution of 1,3,5-benzenetricarbonyltriazide was gradually heated to 120 C and stirred for 2 h. The 1,3,5-triisocyanatobenzene was formed in the solution, which was thencooled to 80 C and used as such without characterizations.
With sodium azide In N,N-dimethyl-formamide at 20℃; for 2h;
With sodium azide In dichloromethane; water at 0 - 20℃; for 3h; Synthesis of 1,3,5-Triisocyantobenzene 1,3,5-Triisocyantobenzene was synthesized by following a modified procedure of M. C.Davis (Ref. 11 in the manuscript). A 500-mL round bottomed flask equipped with magnetic stir bar was charged with 35 mL of H2O and 10.73 g sodium azide (165 mmol, 3.3 equiv.). The mixture was allowed to stir at room temperature until all solid dissolved. The flask was stirred in an ice bath while a solution of 13.20 g 1,3,5-tribenzenecarbonyl chloride (50 mmol,1.0 equiv.) in 150 mL of 1,2-dichloroethane was added by addition funnel over 30 min. The cooling bath was removed, and the mixture was stirred at room temperature for 2.5 hours.The aqueous phase was washed once with 25 mL of 1,2-dichloroethane. The organic phases were pooled and dried over anhydrous MgSO4 for 15 min. The drying agent was removed by filtration through filter paper into a 500 mL round-bottomed flask equipped with a magnetic stir bar. The mixture was refluxed for 2.5 hours. Rotary evaporation of the solvent gave 7.50 g (77%) of white solid as a crude product. Recrystallization in n-hexane to give the title compound as needle white crystals 5.1 g (68%).
With sodium azide In tetrahydrofuran; water at 0℃; for 2h; Compound A. Benzene-1,3,5-tris(tris(trimethylsiloxy)silylpropylurea) Compound A. Benzene-1,3,5-tris(tris(trimethylsiloxy)silylpropylurea) (0060) (0061) Sodium azide (1.75 g, 26.919 mmol, 7 equiv.) was dissolved in 10 mL of deionized water and cooled to 0° C. Separately, 1,3,5-benzenetricarbonyl chloride (1.006 g, 3.789 mmol, 1 equiv.) was dissolved in 10 mL of tetrahydrofuron (THF) and cooled to 0° C. The acid chloride solution was added to the stirring sodium azide solution resulting in the formation of 1,3,5-benzenetricarbonyl azide as a white precipitate. The mixture was stirred at 0° C. for 2 hours behind a blast shield at which point 200 mL of cold toluene and 10 mL of water were added to dissolve all solids. The toluene layer was isolated, washed with water (3×80 mL), saturated aqueous brine (80 mL), dried over magnesium sulfate (MgSO4) and filtered. The filtrate was collected and transferred to a round bottom flask fitted with a reflux condenser connected to a nitrogen inlet and heated to 100° C. for several hours until gas evolution (N2 extrusion) ceased. The solution was then removed from the oil bath and aminopropyltris(trimethylsiloxy)silane (4.022 g, 11.369 mmol, 3.00 equiv.) was added to the hot toluene solution and stirred vigorously overnight. As the mixture cooled to room temperature, it became hazy and the viscosity of the solution increased. The volatiles were then removed under vacuum to produce the intended product as a pale yellow solid (3.291 g, 2.607 mmol, 69% yield). 1H NMR (CDCl3, 400.13 MHz) δ (ppm): 8.24 (broad s, 0.5H, NH), 8.72 (broad s, 3.4H, HAr), 5.38 (broad s, 0.6H, NH), 3.15 (broad s, 4.9H, NHCH2), 1.55 (broad s, 9.0H, CH2CH2Si), 0.46 (broad s, 6.0H, CH2Si), 0.30 to -0.15 (84.0H, SiMe). 13C NMR (CDCl3, 100.62 MHz) δ (ppm): 43.20, 24.25, 11.95, 1.85, 1.74. (0062) Solubility in CO2 and thickening efficacy of Compound A was assessed and the results are shown in Tables 1 and 2 below. As used herein, the term “cloud point” refers to the pressure at which the material begins to precipitate from an optically transparent solution in dense CO2 at a given temperature to form a cloudy, optically opaque mixture. [table-us-00001-en] TABLE 1 Cloud Point for Compound A. Amount of Co- Pressure/ Compound Solvent CO2 Temperature 1.6 wt. % 48.4 wt. % 50 wt. % 1280 psi 25° C.; hexanes 2200 psi 70° C. 1.3 wt. % 38.7 wt. % 60 wt. % 8800 psi 25° C.; hexanes 6100 psi 74° C. 0.5 wt. % 39.5 wt. % 60 wt. % >800 psi hexanes 0.1 wt. % 25 wt. % 74.9 wt. % FontWeight="Bold" FontSize="10" Insoluble up to 80° C. hexanes 0.1 wt. % - 99.9 wt. % FontWeight="Bold" FontSize="10" Insoluble [table-us-00002-en] TABLE 2 Viscosity Effects of Compound A. Amount of Co- Pressure/ Viscosity Compound Solvent CO2 Temperature 320X increase 1.6 wt. % 48.4 wt. % 50 wt. % 25° C. hexanes 100X increase 1.3 wt. % 38.7 wt. % 60 wt. % 25° C. hexanes 14.4X increase 0.5 wt. % 39.5 wt. % 60 wt. % 25° C. hexanes and 8000 psi 12.8X increase 0.5 wt. % 39.5 wt. % 60 wt. % 25° C. hexanes and 6000 psi (0063) Compound A is also soluble in NGLs and increases the viscosity of NGLs. For example, the cloud point for 1.5 wt. % of Compound A in 98.5 wt. % butane was at 192 psi at 80° C., with 2× increase in viscosity; at 154 psi at 60°, with 10× increase; at 124 psi at 40° C., with 50× increase; and at 65 psi at 25° C., with 300× increase in viscosity.

  • 21
  • [ 4422-95-1 ]
  • [ 351-50-8 ]
  • 2-[4,6-bis[(1-carboxy-2-imidazolyl)ethylcarbamoyl]benzenecarbonyl]amino-3-imidazolylpropionic acid [ No CAS ]
  • 22
  • [ 1849-25-8 ]
  • [ 4422-95-1 ]
  • N,N',N''-tris-[4-(phenylethynyl)phenyl]-1,3,5-benzenetricarboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In dichloromethane for 0.166667h;
  • 23
  • [ 4422-95-1 ]
  • [ 5351-23-5 ]
  • C30H24N6O9 [ No CAS ]
YieldReaction ConditionsOperation in experiment
64% With triethylamine In N,N-dimethyl-formamide at 0 - 20℃;
56% With triethylamine In N,N-dimethyl-formamide at 0℃; for 1h; 4 A solution of 1,3,5-benzenetricarbonyl trichloride (0.56 g, 2.1 mmol) in DMF (5 mL) was added dropwise into a solution of p-hydroxybenzoic hydrazide (1.2 g, 7.8 mmol) and triethylamine (0.9 mL) in DMF (15 mL). The solution was stirred at 0° C. for 1 hour, and then stirred at room temperature for another hour. The hydrochloric salt of triethylamine was removed by filtration. The filtrate was added to distilled water. The desired product precipitated as white solids. The precipitate was filtered and dried in vacuum oven (0.7 g, yield 56%). 1H NMR (200 MHz, DMSO-d6): δ 10.7 (s, 3H); 10.4 (s, 3H); 10.2 (s, 3H); 8.6 (s, 3H), 7.8 (d, 6H, J=8.0 Hz); 7.3 (d, 6H, 8.0 Hz) ppm; R (KBr): 3249, 1657, 1608 cm-1.
  • 24
  • [ 21717-29-3 ]
  • [ 4422-95-1 ]
  • [ 797818-00-9 ]
  • 25
  • [ 57260-73-8 ]
  • [ 4422-95-1 ]
  • [ 862299-07-8 ]
YieldReaction ConditionsOperation in experiment
82% With N-ethyl-N,N-diisopropylamine In tetrahydrofuran for 2h; Inert atmosphere;
82% In tetrahydrofuran for 2.16667h; Inert atmosphere; 1.1.a a) Synthesis of 1,3,5-tri-tert-butyl ((benzenetricarbonyltris(azanediyl)) tris(ethane-2,1-diyl))tricarbamate. a) Synthesis of 1,3,5-tri-tert-butyl ((benzenetricarbonyltris(azanediyl)) tris(ethane-2,1-diyl))tricarbamate. In a two-neck round bottom flask fitted with a stirrer bar, and a N2 inlet and outlet, 500 mg of 1,3,5-benzenetricarbonyl trichloride (1.88 mmol, 1 equivalent (eq.)) was dissolved in 12 mL of anhydrous THF. N,N',N"-diisopropylethylendiamine (DIEA) (803.31 mg, 6.22 mmol, 3.3 eq.) was added to the reaction mixture followed by drop-wise addition of N-Boc-ethylendiamine (1.34 g, 6.22 mmol, 3.3 eq.) over a period of 10 min. The reaction was then left to proceed for 2 hours. After that time, the solvent was completely removed under vacuum. The product was re-dissolved in chloroform and washed 3 times with deionized water (ddH2O), and 3 times with acidic water (pH∼3). Finally, the organic phase was isolated under vacuum and the product was recrystallized 3 times from THF/Methanol/Hexane yielding a white crystalline solid. The product was then dried under high vacuum and stored at -20 °C. Yield: 82 %. 1H NMR (300 MHz, DMSO) δ 8.68-8.65 (m, 3H), 8.41 (s, 3H), 6.92-6.88(m, 3H), 3.34-3.31 (m, 6H), 3.16-3.13 (m, 6H), 1.37 (s, 27H). C NMR (75 MHz, CDCl3) δ 166.80 (C=O), 156.84 (C=O), 134.58 (CAr quaternary), 128.47 (CHAr), 79.57 (C quaternary), 40.93 (CH2), 40.43 (CH2), 28.45 (CH3).
74% With pyridine In dichloromethane at 20℃; Cooling with ice; 1 Synthesis of compound 4. General procedure: (See Matsuura, K.; Murasato, K.; Kimizuka, N. J. Am. Chem.Soc: 2005, 127, 10148-10149). To a solution of compound 2 (1.88 mmol) in CH2CI2 (30 mL) was added 10 mL of pyridine and cooled in an ice bath. A solution of compound 3 (7.52 mmol ) in CH2CI2 (30 mL) was added dropwise with stirring. The reaction mixture was then allowed to warm to RT, diluted with 100 mL of CH2CI2 and washed twice with 50 mL of water, 50 mL of saturated NaHCCb, and 50 mL of brine. The solution was dried over solid MgS04for 2 h and concentrated. The residue was purified by column chromatography using a CombiFlash Rf system with a RediSep Gold Resolution silica column (Teledyne Isco) with gradient eiution from 100% CH2CI2 to Ci-hCh eOHTNf-hOH (75/22/3 by volume) to give compound 4, Yield: n 2. 74%, n 3, 68%; n 4. 65%, n 5, 69%; n 6, 81%; n 7. 37%, n 8, 61%.
65% With triethylamine In dichloromethane at 20℃; for 24h;

  • 26
  • [ 4422-95-1 ]
  • [ 78603-95-9 ]
  • N,N',N''-tris[1'-(S)-isopropyl-2',2'-diphenyl-2'-hydroxyethyl]-1,3,5-benzene-tricarboxamide [ No CAS ]
  • 27
  • [ 504-24-5 ]
  • [ 4422-95-1 ]
  • [ 725274-03-3 ]
YieldReaction ConditionsOperation in experiment
97% In N,N-dimethyl-formamide at 20℃; 1 1. Synthesis of DTA Take 3.2 mmol of 4-aminopyridine (0.300g), dissolve in 15mL DMF solution, then add 1mmol of trimesic acid chloride (0.264g) to DMF solution, react at room temperature for 12~14h (overnight), and then use DMF and water were recrystallized to give 0.422 g of 4-aminopyridine functionalized trimesic acid chloride (DTA) in a yield of 97%. Figure 10 is a hydrogen spectrum of DTA.
97% In N,N-dimethyl-formamide at 20℃; 1.1 Example 1 Preparation and Application of Rare Earth Metal Xerogel 1. Preparation of 4-aminopyridine functionalized perylene trimimide:Take 3.2 mmol of 4-aminopyridine (0.300 g) and dissolve in 15 mL of DMF solution.Then, 1 mmol of trimesoyl chloride (0.264 g) was added dropwise to the DMF solution, and the reaction was carried out at room temperature for 12 to 14 hours (overnight).Recrystallization from DMF and water gave 0.422 g of 4-aminopyridine functionalized benzene phthalimide with a yield of 97%.
96% In N,N-dimethyl-formamide at 20℃; for 12h;
96% With TEA at 20℃; for 20h;
92% With triethylamine In tetrahydrofuran for 48h; Heating;
91.5% With triethylamine In tetrahydrofuran at 0℃; for 48h; Reflux;
90% With triethylamine In N,N-dimethyl-formamide at 20℃; for 24h; 2.2 Synthesis and characterization of TA Dissolving the 1,3,5-benzenetricarbonyl trichloride (0.2655g, 1.0mmol) with DMF (10mL), then the solution was dropwise added to a mixture of 4-aminopyridine (0.3106g, 3.3mmol) and TEA (1mL) in DMF (20mL). The reaction mixture was stirred at room temperature for 24h. Recrystallization of TA after the reaction was completed, and then dried under vacuum. Yield: 90% (0.3943g). M.p.: 270-272°C. 1H NMR (400MHz, DMSO-d6), δ/ppm: 10.98 (s, 3H), 8.79-8.75 (t, J=8.6Hz, 3H), 8.55-8.52 (t, J=5.4Hz, 6H), 7.84-7.82 (t, J=4.4Hz, 6H). 13C NMR (151MHz, DMSO-d6), δ/ppm: 166.05, 165.66, 150.87, 150.78, 146.26, 146.13, 145.41, 135.38, 134.92, 132.15, 131.03, 114.60, 109.24. HRMS: m/z [TA+H]+ calcd for C24H19N6O3, 439.1519; found 439.1515.
85% With triethylamine In N,N-dimethyl-formamide at 20℃; for 12h; 1.2 (2) Synthesis of TCP In a solvent of 30 ml DMF, 0.7528 g (8 mmol) of 4-aminopyridine was added until it was completely dissolved.Then, 1,3,5-benzenebenzenetricarboxylic acid chloride (0.5278 g, 2 mmol, 2 drops in about 1 minute) was added dropwise thereto by a constant pressure dropping funnel, and triethylamine was used as an acid binding agent (1.5 mL) at room temperature. ) reaction 12h;After the reaction is completed, distilled water is added under heating to recrystallize; drying,The white product is obtained as a supramolecular compound TCP.The yield is 85%,
81% With triethylamine In tetrahydrofuran for 7h;
78.37% With triethylamine In tetrahydrofuran at 0℃; Inert atmosphere; 2.2. Synthesis of 1 General procedure: The THF solution of 1,3,5-benzenetricarbonyl chloride (0.5310 g, 2 mmol) was added dropwise to the THF solution (25 mL) of 3-aminopyridine (0.5647 g, 6 mmol) and triethylamine (1.0119 g, 10 mmol) at 0 °C with continuous stirring under nitrogen atmosphere. The solution was stirred overnight. THF was distilled off and the solid product thus obtained was washed with water and recrystallized from MeOH. Yield: 85%. This product was crystallized from MeOH as described in the results and discussion and obtained the crystals of three forms.
4.2 g With triethylamine In tetrahydrofuran at 0 - 20℃; for 10h;
With dmap In N,N-dimethyl acetamide at 20℃; for 120h;
With triethylamine In tetrahydrofuran at 0 - 20℃; for 7h; 1 The 36mmol (3.4g) 4-aminopyridine was added to 36mmol (5.0mL) of triethylamine and 40 ml of THF (tetrahydrofuran) in mixture, 12mmol (3.22g) was dissolved 12mL THF the acid chloride prepared acid chloride solution.At 0 °C conditions, the acid chloride solution was slowly added dropwise to a mixture of 4-aminopyridine, was added to continue 12mmol (1.7mL) of triethylamine, the temperature in the mixing temperature rising rate of 0.2 / min is gradually raised to room temperature, reaction 7 hours. Brown crude product obtained was suction filtered, THF washed, dried, recrystallized in 140mLDMSO (dimethylsulfoxide) and stirred for 1 hour 300mL of water, and dried in vacuo. The purpose of 1.0g crude amide 1.0g 200-300 hole zcx-2 over a silica gel column uniformly mixed sample, 30g through the column of silica gel packed in 35 * 500 (inner diameter × length in mm) chromatography column; use of 1:3 a mixture of methanol and chloroform as the eluent was subjected to column chromatography; eluent through the column will post on a rotary evaporator at 63 °C vacuum distillation to give a colorless granular crystals; and dried under vacuum to obtain a terephthalic loyal adsorbed organic porous material.

Reference: [1]Current Patent Assignee: NORTHWEST NORMAL UNIVERSITY - CN110041251, 2019, A Location in patent: Paragraph 0024
[2]Current Patent Assignee: NORTHWEST NORMAL UNIVERSITY - CN110054586, 2019, A Location in patent: Paragraph 0023
[3]Fan, Yan-Qing; Liu, Juan; Chen, Yan-Yan; Guan, Xiao-Wen; Wang, Jiao; Yao, Hong; Zhang, You-Ming; Wei, Tai-Bao; Lin, Qi [Journal of Materials Chemistry C, 2018, vol. 6, # 48, p. 13331 - 13335]
[4]Wei, Tai-Bao; Qi, Li-Hua; Zhang, Qin-Peng; Zhang, Wen-Huan; Yao, Hong; Zhang, You-Ming; Lin, Qi [New Journal of Chemistry, 2020, vol. 44, # 29, p. 12531 - 12537]
[5]Hong, Seunghee; Zou, Yang; Moon, Dohyun; Lah, Myoung Soo [Chemical Communications, 2007, # 17, p. 1707 - 1709]
[6]Ahmed, Manan; Xie, Zixi; Thoonen, Shannon; Hua, Carol; Kepert, Cameron J.; Price, Jason R.; Neville, Suzanne M. [Chemical Communications, 2021, vol. 57, # 1, p. 85 - 88]
[7]Zhang, You-Ming; Zhu, Wei; Zhao, Qi; Qu, Wen-Juan; Yao, Hong; Wei, Tai-Bao; Lin, Qi [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2020, vol. 229]
[8]Current Patent Assignee: NORTHWEST NORMAL UNIVERSITY - CN109053728, 2018, A Location in patent: Paragraph 0027; 0028
[9]Hasegawa, Shinpei; Horike, Satoshi; Matsuda, Ryotaro; Furukawa, Shuhei; Mochizuki, Katsunori; Kinoshita, Yoshinori; Kitagawa, Susumu [Journal of the American Chemical Society, 2007, vol. 129, # 9, p. 2607 - 2614]
[10]Location in patent: experimental part Rajput, Lalit; Biradha, Kumar [Journal of Molecular Structure, 2011, vol. 991, # 1-3, p. 97 - 102]
[11]Luo, Xu-Zhong; Jia, Xin-Jian; Deng, Ji-Hua; Zhong, Jin-Lian; Liu, Hui-Jin; Wang, Ke-Jun; Zhong, Di-Chang [Journal of the American Chemical Society, 2013, vol. 135, # 32, p. 11684 - 11687]
[12]Zhao, Xiang; Bu, Xianhui; Zhai, Quan-Guo; Tran, Huy; Feng, Pingyun [Journal of the American Chemical Society, 2015, vol. 137, # 4, p. 1396 - 1399]
[13]Current Patent Assignee: GANNAN NORMAL UNIVERSITY - CN103896832, 2016, B Location in patent: Paragraph 0026; 0028; 0029
  • 28
  • [ 22348-32-9 ]
  • [ 4422-95-1 ]
  • [ 909698-82-4 ]
  • 29
  • [ 4422-95-1 ]
  • [ 534-85-0 ]
  • [ 950766-71-9 ]
YieldReaction ConditionsOperation in experiment
98% In tetrahydrofuran at 20℃; Industrial scale; 1.1 Step One Step One[0025]Dissolved 289.00 G of N-Phenyl-o-Phenylenediamine in 1 L of THF and reached bronzing solution. Then dissolved in 126.10 G of trimesoyl Chloride at room temperature, the solution turned to be brownish black and with no change in the temperature. Then the solution after stable overnight were poured into 3 L of water, a great mass of oily matter occurred. After cooled and lumped, filtered and dried, 450 G of brown solid reached, with 98% of yield rate.
70% In methylpyrrolidin-2-one; 1- (NMP) at 20 - 50℃; for 2h; Heating / reflux; 1 N-phenyl-1,2-phenylenediamine (0.541 mol) was combined with 1,3,5-benzene-tricarbonyl chloride (0.181 mol) in 1.8 L N-methylpyrrolidone (NMP) and stirred for 2 hrs at room temperature and then heated to 50° C. overnight. The reaction mixture was cooled to room temperature and precipitated into water (5 parts water to 1 part reaction mixture) and filtered through a medium frit then dried in a vacuum oven. Approx. 138 g of dried solid material was combined with POCl3 (0.5 kg) and carefully warmed to 98° C. for 14 hrs. The mixture was cooled to room temperature, then precipitated into stirred ice chips and water (5 parts ice and one part reaction mixture). The quenched material was neutralized with 50% NaOH to pH 9, filtered through a medium frit, and then dried in a vacuum oven. The solid was dissolved in dichloromethane (DCM), eluted through a silica plug and then purified by silica column chromatography using ethyl acetate/hexanes. 58.51 g of solid were isolated by concentrating the eluant almost to dryness, then filtering followed by drying with vacuum. The average yield for each of the two steps was 70%.
In 1-methyl-pyrrolidin-2-one at 20 - 50℃; for 2.5h;
  • 30
  • [ 4422-95-1 ]
  • [ 1664-40-0 ]
  • N-1,3,5-tris[2-(phenylamino)ethyl]benzene-1,3,5-tricarboxylamide [ No CAS ]
  • 31
  • [ 4422-95-1 ]
  • [ 178949-98-9 ]
  • N,N',N''-tris[(S)-(benzyl)(octyloxycarbonyl)methyl]benzene-1,3,5-tricarboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With triethylamine In dichloromethane at 0 - 20℃; for 3h;
50% With triethylamine In dichloromethane at 20℃; for 20h; benz-am-phe (MdL064) To a cooled solution of MdL063 (2.0 g, 7.2 mmol) and triethyl amine (0.73 g, 7.2 mmol) in dry CH2Cl2 (50 ml) was added a solution of 1,3,5-benzenetricarbonyl trichloride MdL012 (0.64 g, 2.4 mmol) in dry CH2Cl2 (5 ml). The solution was slowly brought to room temperature and stirred for 20 h. Subsequently CHCl3 (20 ml) was added and the solution was extracted successively with dilute HCl, water, 10% sodium carbonate, water, brine. The solution was dried over MgSO4 and the solvents were evaporated in vacuo, yielding a sticky solid. Column chromatography (CH2Cl2/MeOH; 100/1) on silica gel yielded MdL064 (1.2 g, 1.21 mmol, 50 %) as a white sticky solid. 1H NMR (DMSO-d6): δ = 9.12 (d, 3H, 3J = 7.3 Hz), 8.39 (s, 3H), 7.25 (m, 15H), 4.67 (m, 3H), 4.01 (t, 6H, 3J = 6.4 Hz), 3.13 (d, 6H, 3J = 8.4 Hz), 1.48 (s, 6H), 1.17 (s, 30H), 0.80 (t, 9H, 3J = 6.6 Hz); 13C NMR (DMSO-d6): δ = 171.55, 165.54, 137.58, 134.16, 129.29, 129.02, 128.26, 126.49, 64.57, 54.62, 36.32, 31.19, 28.58, 28.04, 25.28, 22.07, 13.92; C60H81N3O9: calcd. C 72.92, H 8.26, N 4.25; found: C 72.83, H 8.33, N 4.25.
1.2 g With triethylamine In dichloromethane at 20℃; for 20h;
  • 32
  • [ 4422-95-1 ]
  • [ 4464-18-0 ]
  • 34
  • [ 3047-32-3 ]
  • [ 4422-95-1 ]
  • [ 874108-45-9 ]
YieldReaction ConditionsOperation in experiment
With dmap; triethylamine; In dichloromethane; at 0 - 10℃; for 24h; The initial charge was added to a 500-mL 4-neck round bottom flask: 3-ethyl-3-(hydroxymethyl) oxetane (40 g, 0.344 mol), triethylamine (34.809 g, 0.344 mol), dimethylaminopyridine (4.203 g, 0.034 mol) and dichloromethane (300 mL). The reaction vessel was equipped with an overhead mixer and condenser. Stirring was continued until the mixture became homogeneous. The temperature was kept between 0° and 10°C. 1,3,5-Benzenetricarbonyl trichloride (30.442 g, 0.115 mol) was dissolved into dichloromethane (100 mL) and the mixture was charged to the flask dropwise over a period of one hour. The reaction was monitored by FT-IR analysis for the consumption of carbonyl group in acid chloride (peak at 1801 cm-1) and the formation of ester group in product (peak at 1736 cm-1). The reaction was completed after 24 hours. The reaction mixture was washed with water (5 x 50 mL). The organics were dried over MgSO4, filtered, and the solvent was evaporated off at bath temperature of 50°C. Product was mixed with ethyl acetate (300 mL) and temperature was reduced below -30°C by dry ice. An insoluble white solid (product) precipitated out. Product was filtered and washed with hexane (3 x 30 mL) to afford a white solid with a melting point of 97°C. The NMR for this compound is shown in Figure 4.
  • 35
  • [ 159-66-0 ]
  • [ 4422-95-1 ]
  • Ph(CO-SBF)3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With aluminum (III) chloride; In dichloromethane; at 20℃; for 2.5h;Heating; Reflux; To 1.26 g 1,3,5-benzenetricarbonyl trichloride (4.74 mmols) in 20 ml CH2Cl2, 843 mg of finely pulverized anhydrous AlCl3 (6.32 mmols) is added at 15 C. (water-ice bath) (yellow colour). A solution containing 500 mg <strong>[159-66-0]9,9'-spirobifluorene</strong> (1.58 mmols) in 10 ml CH2Cl2 is added dropwise and under stirring within 30 minutes and is allowed to reach RT (green-orange-red colour). Then, the mixture is heated under reflux and the stirring is maintained for two more hours. After treatment with water and ice and then with diluted HCl the organic phase is separated. The organic extracts are treated with saturated sodium carbonate, washed with water and dried on anhydrous sodium sulphate; a yellow waxy liquid is obtained. Column chromatography, eluent 40% CH2Cl2-hexane (plate at 60% with the same eluents).13C-NMR (CDCl3, 50 MHz, delta [ppm] vs SiMe4): 191.5 (CO), 65.6 (spiro C).
To 1.26 g 1,3,5-benzenetricarbonyl trichloride (4.74 mmols) in 20 ml CH2CI2, 843 mgof finely pulverized anyhydrous AICI3 (6.32 mmols) is added at 15C (water-ice bath)(yellow colour). A solution containing 500 mg <strong>[159-66-0]9,9'-spirobifluorene</strong> (1.58 mmols) in10.ml CH2CI2 is added dropwise and under stirring within 30 minutes and is allowedto reach RT (green-orange-red colour). Then, the mixture is heated under reflux andthe stirring is maintained for two more hours. After treatment with water and ice andthen with diluted HCI the organic phase is separated. The organic extracts aretreated with saturated sodium carbonate, washed with water and dried on anhydroussodium sulphate; a yellow waxy liquid is obtained. Column chromatography, eluent40% CH2CI2-hexane (plate at 60% with the same eluents).13C-NMR (CDCI3> 50 MHz, 5 [ppm] vs SiMe4): 191.5 (CO), 65.6 (spiro C).
  • 36
  • [ 4422-95-1 ]
  • 2-(2-(2-(5-(2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-6-yl)pentanoylamino)ethoxy)ethoxy)ethylammonium 2,2,2-trifluoroacetate [ No CAS ]
  • N,N',N''-tris(8-N-Boc-3,6-dioxaoctanyl)benzene-1,3,5-tricarboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% With triethylamine In dichloromethane at 0 - 20℃; for 10h; 6.4 Reaction Step 4,; Preparation of N,N',N-tris(8-N-Boc-3.6-dioxaoctanyl)benzene-1,3,5-tricarboxamide To a solution containing 0.28 g (1.05 mmol) of benzene-1,3,5-tricarbonyl trichloride in 10 mL CH2Cl2 at 0° C. was added 0.74 g (2.98 mmol) 8-N-Boc-3,6-dioxa-octaneamine and 0.70 9 (6.91 mmol) triethylamine in 5 mL CH2Cl2. The reaction mixture was stirred under argon for 10 hours at ambient temperature and the volatile material was evaporated under reduced pressure. The residue was redissolved in 150 mL CH2Cl2, washed with 20 mL water, dried over anhydrous Na2SO4, and evaporated to yield 0.82 g (87%) of the desired product as a tacky solid. 1H NMR (CDCl3) δ 8.33 (s, 3H), 7.67 (s, ArCONH, 3H), 5.45 (s, Boc-NH, 3H), 3.65 (m, 24H), 3.53 (m, 6H), 3.26 (m, 6H), 1.39 (s, 27H).
  • 37
  • [ 651354-65-3 ]
  • [ 4422-95-1 ]
  • C174H300N42O60 [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With triethylamine In dichloromethane at 20℃; 14.1 To a solution of dendrimer amine 5 (1.0 g, 0.79 mmol) and Et3N (0.13 mL, 0.95 mmol) in 10 mL of CH2Cl2, was added dropwise a solution of 1,3,5-benzenecarbonyl trichloride (55 mg, 0.21 mmol) in CH2Cl2 at room temperature. The mixture was stirred overnight and poured into ice water (50 mL). The resulting mixture was extracted with CH2Cl2 (2×50 mL). The organic phase was washed with 1N HCl (2×50 mL), saturated NaHCO3 (50 mL), brine (50 mL) and H2O (2×50 mL), and evaporated under reduced pressure. The resulting residue was purified by flash column chromatography (on silica gel, MeOH:CH2Cl2=1:10) affording 0.73 g (89%) of the desired Boc-protected nonaguanidine compound (45) as a colorless foam-shaped solid. 1H NMR (CDCl3): δ 11.40 (s, 9H, NH), 8.64 (s, 9H, NH), 8.49 (s, 3H, ArH), 8.01 (s, 3H, NH), 7.92 (s, 9H, NH), 6.72 (s, 3H, NH), 3.65 (m, 36H, CH2O), 3.56 (m, 24H, CH2NHCO), 3.38 (m, 18H, CH2NH), 2.54 (m, 6H, CH2CO), 2.40 (m, 18H, CH2CO), 1.47 (s, 81H, t-Bu), 1.46 (s, 81H, t-Bu); 13C NMR (CDCl3): δ 171.88, 171.71, 171.63, 166.36, 163.01, 157.13, 157.07, 152.96, 135.37, 128.84, 83.63, 83.56, 79.64, 69.59, 67.60, 59.96, 40.71, 37.34, 36.73, 28.60, 28.36; ESI-MS m/z 3936 [Mavg].
  • 38
  • [ 4422-95-1 ]
  • [ 99-09-2 ]
  • [ 940301-02-0 ]
YieldReaction ConditionsOperation in experiment
91% In acetonitrile at 85℃;
87% With triethylamine In acetonitrile at 20℃; for 3h; 3.3a A solution of 8 (3.0 g, 11 mmol) in acetonitrile (40 ml) was added drop wise to a solution of 9 (5.2 g, 38 mmol) and Et3N (5.2 ml, 38 mmol) in acetonitrile (90 ml) under vigorous stirring and argon atmosphere. After stirring at r t for 3 hours the solvents were removed on a rotary evaporator. The crude residue was suspended in water, filtered off and washed several times with water. The yellow precipitate was washed several times with diethyl ether to remove all residual 2 giving 10 as a pale solid (5.6 g, 87 %). The structure was confirmed by LC-MS.
  • 39
  • [ 99-31-0 ]
  • [ 4422-95-1 ]
  • [ 404018-62-8 ]
YieldReaction ConditionsOperation in experiment
95.8% With dmap In N,N-dimethyl acetamide for 96h;
95% With dmap In N,N-dimethyl acetamide at 25℃; for 12h; Inert atmosphere; 1 In a reactor equipped with a stirrer and a nitrogen inlet tube,In a nitrogen atmosphere, 5-aminoisophthalic acid (103 parts), N, N-dimethyl-4-aminopyridine (DMAP) (7 parts) and N, N- dimethylacetamide (DMAc) (1800 parts) were added and stirred . Thereafter, 1,3,5-benzenetricarbonyl trichloride (50 parts) was slowly added, and the reaction was carried out for 12 hours while maintaining the reaction temperature at 25 ° C. After completion of the reaction, the reaction solution was poured into pure water (8000 parts), the precipitate was separated by filtration and vacuum dried at 50 ° C. to obtain 125 parts (95%) of intermediate product 1.
88% With triethylamine In acetone for 16h;
  • 40
  • [ 4097-88-5 ]
  • [ 4422-95-1 ]
  • [ 1032197-99-1 ]
YieldReaction ConditionsOperation in experiment
15% With triethylamine In dichloromethane Inert atmosphere; Cooling with acetone-dry ice;
  • 41
  • [ 4422-95-1 ]
  • [ 107-19-7 ]
  • [ 871830-29-4 ]
YieldReaction ConditionsOperation in experiment
91% With dmap In dichloromethane at 0℃; Procedure for the synthesis of tri(prop-2-yn-1-yl)benzene-1,3,5-tricarboxylate (2) To a stirred solution of propargyl alcohol (3.3 mmol) and 4-dimethylaminopyridine (3.3 mmol) in 30 mL of dichloromethane, benzene-1,3,5-tricarbonyl trichloride (1 mmol; dissolved in dichloromethane) was added drop wise at 0 °C. The stirring of reaction mixture was continued till the completion of reaction, as monitored by TLC. After completion of the reaction, the reaction mixture was diluted with dichloromethane and the organic layer was washed with 2 N sulphuric acid (2 × 10 mL), water (2 × 10 mL) and brine (10 mL) and dried over anhydrous sodium sulphate. Dichloromethane was evaporated in vacuum to obtain the product. Tri(prop-2-yn-1-yl)benzene-1,3,5-tricarboxylate (2): Off white solid, yield: 91 %, m.p.: 198-200 °C. IR (KBr, νmax,cm-1): 3287, 3084 (str.), 2126 (C=C str), 1736 (C=O str., ester), 1655, 1609 (C=O str., ester), 1441, 1371, 1325, 1271, 1233(C-O str., ester), 1152, 1107 (C-O str., ester), 999, 959, 932, 737, 689, 646). 1H NMR (CDCl3, 400 MHz): δ 2.58 (t, 3H, alkyne CH), 5.01 (d, 6H, OCH2), 8.98 (s, 3H, Ar-H). 13C NMR(CDCl3, 100 MHz): δ 53.15 (OCH2), 75.64 (CH acetylene), 77.11 (C acetylene), 130.78 (Ar-C), 135.30, (Ar-C), 164.00(C=O). HRMS: m/z (M+H)+ cacld. for C18H12O6: 325.0712,found: 325.0757.
90% With pyridine In 1,2-dichloro-ethane at 10 - 20℃;
75% With triethylamine In tetrahydrofuran at 0 - 40℃; for 19.5h;
75% With triethylamine In tetrahydrofuran at 0 - 40℃; for 19.5h; 2 2.2. Synthesis of triprop-2-ynyl benzene-1,3,5-tricarboxylate (A) Propargyl alcohol (3.2 mL, 55 mmol) and triethylamine (697 μL, 5 mmol) were dispersed in 20mL of THF in a 100 mL round bottom flask. The mixture was cooled to 0 °C in an ice-water bath. 1,3,5-Benzenetricarbonyl trichloride (982 μL, 5.5 mmol) was dissolved in 15 mL of THF and was introduced into the reaction mixture slowly over a period of 30 min. Further the mixture was stirred at 0 °C for 1 h and then at 40 °C for 18 h. White precipitate obtained was then filtered out and filtrate was collected. The solvent was evaporated from the filtrate, under vacuum. The product obtained was redissolved in dichloromethane and then washed with 10% HCl, aqueous NaHCO3 and finally twice with distilled water. Dichloromethane was subsequently removed by rotary evaporation and the crude product was purified by column chromatography (Chen et al., 2009). Yield 1.37 g, 75%.
1.32 g With triethylamine In dichloromethane at 0 - 20℃; for 24h;

  • 42
  • [ 678-39-7 ]
  • [ 4422-95-1 ]
  • C19H7Cl2F17O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine; In HCFC225; at 20℃;Inert atmosphere; [Example 1] Preparation of the acryl-containing fluorine-based compound 1; [59] 5.37 g of 1,3,5-benzenetricarboxyl trichloride and 30 mL of HCFC225 were added to the 100 mL flask including the the thermometer and agitating apparatus, and agitated at room temperature and a nitrogen atmosphere. After 1,3,5-benzenetricarboxyl trichloride was dissolved in HCFC225, 11.40 g of perfluoro alcohol (average molecular weight 564 g / mol) was added to the reaction solution. Subsequently, 2.25 g of triethylamine was slowly dropped. After the reaction solution was agitated for 1 hour, 5.31 g of 2-hydroxy ethyl methacrylate was dropped. After 10 min, 5.50 g of triethylamine was slowly dropped. Subsequently, after the agitation for 1 hour, the precipitate was filtered to remove, and HCFC225 was removed by distillation to obtain 21.4 g of the colorless/transparent acryl-containing fluorine-based compound 1. NMR data of the obtained compound are shown in FIG. 1.; [Example 2] Preparation of the silicon-containing fluorine-based compound 2; [61] 5.37 g of 1,3,5-benzenetricarboxyl trichloride and 30 mL of HCFC225 were added to the 100 mL flask including the the thermometer and agitating apparatus, and agitated at room temperature and a nitrogen atmosphere. After 1,3,5-benzenetricarboxyl trichloride was dissolved in HCFC225, 11.40 g of perfluoro alcohol (average molecular weight 564 g / mol) was added to the reaction solution. Subsequently, 2.25 g of triethylamine was slowly dropped. After the reaction solution was agitated for 1 hour, 7.30 g of 3-aminopropyltrimethoxysilane was dropped and agitated for 1 hour. The precipitate of the solution was filtered to remove, and HCFC225 was removed by distillation to obtain 23.4 g of the colorless/transparent silicon-containing fluorine- based compound 2. NMR data of the obtained compound are shown in FIG. 2.
  • 43
  • [ 86-73-7 ]
  • [ 4422-95-1 ]
  • [ 1220890-19-6 ]
YieldReaction ConditionsOperation in experiment
91% With aluminum (III) chloride In carbon disulfide at 0℃; Reflux; 8.1 Example 8. Synthesis of benzene-l,3,5-triyltris((fluorenon-2- yl)methanone)tricofluorenone; Step 1.; 265 mg of anhydrous finely pulverized AICI3 (2.0 mmol) are added to 160 mg of 1,3,5-benzenetricarbonyl trichloride (0.6 mmol) in 10 ml of CS2 at 00C. Then, a solution containing 300 mg of fluorenone (1.8 mmol) in 10 ml of CS2 is added dropwise and is stirred for 30 minutes and the solution is then left to get down to room temperature. The mixture is then heated under reflux and kept stirred for further 3 hours. After treatment with ice, water and dilute HCl, the organic phase is separated. The organic extracts are then treated with a saturated solution of sodium carbonate, washed with water and dried on anhydrous sodium sulphate. The solvent phase is then filtered onto Celite and evaporated under vacuum to yield 362 mg of tricofluorene [benzene-l,3,5-triyltris((9H-fluoren-2-yl)methanone)] (yield 91%). iH-NMR (CDCl3, 200 MHz, δ vs SiMe4): 8.53 (s, 3 H, ArH); 8.07 - 7.31 (me, 21 H, ArH); 3.85 (s, 6H, CH2).13C-NMR (CDCl3, 50 MHz, δ vs SiMe4): 36.87 (CH2); 119.86, 125.03, 125.256, 127.12, 128.26, 134.72, 134.76, 138.79, 140.20, 141.62, 143.16, 143.42, 144.50, 146.71 (aromatic CH and Cq groups); 194.89 (CO).
  • 44
  • [ 259-79-0 ]
  • [ 4422-95-1 ]
  • 1,3,5-tri-(biphenylene-2-carbonyl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
25% With aluminum (III) chloride; In carbon disulfide; at 0℃;Reflux; Example 2: Synthesis of benzene-l,3,5-tri-(-2-carbonyl-<strong>[259-79-0]biphenylene</strong>) (BTCB); 96 mg of finely pulverized anhydrous AlCl3 (P.F. = 133.30; 0.723 mmol) are added to 324 mg of 1,3,5-benzenetricarbonyl trichloride (P.F. = 265.48; 0.219 mmol) in 10 ml of CS2 at 00C (water-ice bath). A solution containing 100 mg of <strong>[259-79-0]biphenylene</strong> (P.F. = 152.19; 0.657 mmol) in 5 ml of CS2 is added dropwise under stirring, in a time period of half an hour, and is left to reach room temperature. Subsequently, it is refluxed and kept under stirring for further 2 hours. It is treated with water and ice, then with dilute HCl and the organic phase is then separated. The organic extracts are pooled, treated with a saturated solution of sodium carbonate, washed with water and dried on anhydrous sodium sulphate. A column chromatography then follows using a mixture of dichloromethane-exane 20% as the eluent (yield D%)1H-NMR (CDCl3, 200 MHz, delta vs SiMe4): 8.24 - 6.68 (me, ArH) 13C-NMR (CDCl3, 50 MHz, delta vs SiMe4): 116.37; 116.96; 118.56;118.97; 129.12; 129.95; 132.98; 133.94; 136.59; 138.48; 149.58; 150.14;151.88; 157.06 (all quaternary aromatic C and aromatic CH groups);193.88 (CO).
  • 45
  • [ 4422-95-1 ]
  • [ 2450-71-7 ]
  • [ 902136-65-6 ]
YieldReaction ConditionsOperation in experiment
100% With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 24h; Inert atmosphere; 11 N,N3,N5-tripropargyltrimesoamide (compound 2-28-1) The reaction flask with drain pump, which leads to the protection of nitrogen, was added 2ml dry methylene chloride was added propargyl amine (27μl, 0.422mmol), was added DIPEA (138.5μl, 0.840mmol) stir, trimesic acid chloride (15.0 μl, 0.0840mmol), stirred at room temperature for about 24h. Methylene chloride was evaporated to dryness, the residue was dissolved in methanol, mixed with silica gel-like, dry-packed, atmospheric pressure and purified by chromatography. Eluent: dichloromethane: methanol = 40:1 → 30:1. As a white solid compound 27.2mg, 100% yield.
73% With dmap; triethylamine In dichloromethane at 0 - 20℃; for 3.25h;
44% With triethylamine In dichloromethane at 0℃; for 3h;
43% With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
43% With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 16h; Inert atmosphere;
0.54 g With pyridine In dichloromethane at 0 - 20℃; for 24h;

  • 46
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  • [ 32854-09-4 ]
  • [ 1233958-04-7 ]
  • 47
  • [ 1008513-62-9 ]
  • [ 4422-95-1 ]
  • [ 1242462-30-1 ]
YieldReaction ConditionsOperation in experiment
100% With dmap; triethylamine In dichloromethane at 0 - 20℃; 1 Synthesis oftris (4-methyl diaryldiazomethane) L 3, 5 -benzene tr jester (19), with reference to Figure 4; A solution of 1,3,5 benzene tricarbonyl trichloride 1 (2.33 g, 8.8mmol) in DCM (10 mL) was cooled to O0C in an ice bath. DMAP (cat. 54mg, 0.4mmol) and triethylamine (12.2 mL, 88mmol) were added to the solution and allowed to cool. Then hydroxymethyl benzophenone diazo 2 (6 g, 26mmol) in DCM (40 mL) was added and stirring maintained as the mixture warmed to room temperature. After 4 hours there was no starting material left by TLC and the reaction was worked up by diluting with DCM (60 mL) and partitioning between DCM and brine. The combined organic layer (200 mL) was dried with MgSO4 filtered and concentrated in vacuo to yield 3 (7.99 g, quant.) as a red solid; vmax (thin film) 2010, 1720, 1220 cm"1.
  • 48
  • [ 926652-68-8 ]
  • [ 4422-95-1 ]
  • [ 1258531-72-4 ]
YieldReaction ConditionsOperation in experiment
75% With tetrabutylammomium bromide; potassium carbonate In dichloromethane at 0 - 20℃; K2CO3 (1.0 g, 7.25 mmoles, 7.7 eq) was dissolved in H2O (12 ml.) and Aliquat (17 mg) and placed in a 100 mL flask. The tri-Boc tetraamine analogue 18 (1.68g: 3.17 mmoles) was dissolved in CH2CI2 (5 mL) was added to the flask. The mixture was cooled to 00C and the triacid chloride 11 (0.25g: 0.9417 mmoles) was dissolved in CH2CI2 (15 mL) and was slowly added dropwise to the flask while stirring. The reaction was warmed to room temperature and stirred for 6 hours. The product was extracted 3 times with CH2CI2. The organic layers were separated, combined and dried over anhydrous sodium sulfate filtered and concentrated to give a viscous pale yellow oil. After high vacuum exposure, the product appeared as a flaky solid (1.33 g). The product was purified by column chromatography (5% MeOH in CH2CI2) to yield 1.24g (75% yield). Compound 19: 1H NMR (CDCI3): δ 8.4 (s, 3H), 4.8 (br s, NH, 3H), 3.5 ( br s, 6H), 3.2 (30H), 1.8-1.2 (m, 120H); 13C NMR(CDCI3): δ 166.4,156.2, 155.7, 135.4, 128.9, 79.5, 79.4, 79.1 , 46.8, 45.8, 41.3, 41.1 , 40.9, 40.3, 40.0, 39.8, 39.3, 29.58, 29.1 , 29.1 , 29.0, 28.6, 28.5, 28.47, 28.0, 27.9, 27.4, 27.1 , 26.9, 26.5, 26.3, 26.1 , 26.0, 25.6; elemental analysis C90H162N12O21 theory C: 61.83; H: 9.34; N: 9.61 ; found C: 61.64; H: 9.31 ; N: 9.38. Using TLC, only one spot was detected using the short wave UV, which was dark blue (Rf = 0.26, 96%CH2CI2, 4% MeOH)
75% With potassium carbonate In dichloromethane; water at 0 - 20℃; for 6h; Inert atmosphere;
  • 49
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  • [ 705281-91-0 ]
  • [ 1258531-67-7 ]
YieldReaction ConditionsOperation in experiment
78% With potassium carbonate In dichloromethane; water at 0 - 20℃; A solution of (4-Amino-butyl)-(4-ferf- butoxycarbonylamino-butyl)-carbamic acid tert-butyl ester 12 (460 mg, 1.28 mmol) and CH2CI2 (3 mL) was prepared. Note: 12 is a known compound (ref: "Total Synthesis of Petrobactin and Its Homologues as Potential Growth Stimuli for Marinobacter hydrocarbonoclasticus, an oil-degrading bacteria." Gardner, R. A.; Kinkade, R.+; Wang, C. ; Phanstiel IV, O. J. Org. Chem. 2004, 69, 3530-3537). A solution of K2CO3 (420 mg, 3.04 mmol) and water (5 ml.) was added to the original mixture. Aliquat (0.10 ml_) was added and the mixture was cooled to O0C. 1 ,3,5-benzenetricarboxylic acid chloride 11 (105 mg, 0.395 mmol) in CH2CI2 (6 ml) was added dropwise to the original mixture and allowed to gradually warm and stir vigorously at rt for 6 hours. TLC (95% CH2CI2, 4% MeOH, 1% NH4OH Rf=O.35) was used to monitor the reaction. After the reaction was complete, the aqueous layer was extracted three times in CH2CI2 and saturated Na2CO3. The organic layers were combined and dried over anhydrous Na2SO4, filtered, and concentrated to give 590 mg of crude product. The crude was subjected to flash column chromatography (95% CH2CI2, 4% MeOH, 1 % NH4OH Rf=0.35) to give 13 (382 mg, 0.310 mmol, 78%). 1H NMR (CDCI3): δ 8.41 (s, 3H), 4.75 (br s, 3H), 3.49 (m, 6H), 3.23-3.06 (m, 18H), 2.78-1.30 (m, 78H).
56% With potassium carbonate In dichloromethane; water at 0 - 20℃; for 6h; Inert atmosphere;
  • 50
  • 1,3-bis(prop-2-yn-1-yloxy)-2-((prop-2-yn-1-yloxy)methyl)propan-2-amine [ No CAS ]
  • [ 4422-95-1 ]
  • [ 1313375-62-0 ]
YieldReaction ConditionsOperation in experiment
68% With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; for 15h; Inert atmosphere;
68% With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; for 15h; Inert atmosphere; 1 Example 1 - Synthesis of the scaffold used to prepare the nonavalent molecules (101) To a solution of alkyne 102 (75 mg, 0.32 mmol) [Z.-J- Li et al. Org. Biomol. Chem. 2014, 41, 8180] and DIPEA (139 μΙ_, 0.81 mmol) in dry CH2CI2 (1 mL), cooled to 0 °C and under nitrogen atmosphere, a solution of 103 (24 mg, 0.09 mmol) in dry CH2CI2 (1 mL) was added. The reaction mixture was stirred at room temperature for 15 h, until a TLC analysis (CH2Cl2:MeOH 10:1 ) showed disappearance of the starting material (flf = 0.96) and formation of a new product (R= 0.84). After washing with HCI 0.5 M (10 mL) and H2O (2x10 mL), the combined organic layers were dried over Na2SO4 and concentrated under reduced pressure. The crude mixture was purified by FCC (hexane:AcOEt 2:1 ) affording pure 101 [M. Chabre, D. Giguere, B. Blanchard, J. Rodrigue, S. Rocheleau, M. Neault, S. Rauthu, A. Papadopoulos, A. A. Arnold, A. Imberty e R. Roy, Chem. - Eur. J., 2011 , 17, 6545-6562] (R = 0.17, 53 mg, 0.060 mmol, 68% yield) as a white solid.
160 mg With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; Inert atmosphere;
  • 51
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  • [ 120207-16-1 ]
  • 52
  • [ 1308332-52-6 ]
  • [ 4422-95-1 ]
  • [ 1399234-66-2 ]
YieldReaction ConditionsOperation in experiment
97% With dmap; triethylamine In dichloromethane at 0℃; for 2h; Inert atmosphere; 18 Example 18: Under nitrogen atmosphere 1.25 grams of benzene-1,3,5-tricarbonyl trichloride dissolved in 5 mL of dry dichloromethane was added dropwise to a pre-cooled 20 mL of dichloromethane solution at 0 °C containing 2.74 grams of 2-hydroxy-1-(3-(hydroxymethyl)phenyl)-2-methylpropan-1-one, 2 mL of Et3N and 50 mg of N,N-dimethylpyridin-4-amine. The mixture was stirred for 2 hrs and gradually warmed to room temperature. The mixture was concentrated and then diluted by 100 mL of ethyl acetate, washed successively by saturated NaHCO3 and brine of half volume. The organic layer was dried and concentrated, and the crude product was further purified by silica gel column chromatography with mixtures of hexane/ethyl acetate (V/V = 2/1) to give the target product as colorless oil (97% yield). 1H NMR (CDCl3, ppm): 8.88 (s, 3H), 8.15 (s, 3H), 8.01 (d, 3H, J = 7.8 Hz), 7.62 (d, 3H, J = 7.5 Hz), 7.46 (dd, 3H, J = 7.8 Hz, J = 7.5 Hz), 5.43 (s, 6H), 4.02 (s, 3H), 1.59 (s, 18H); 13C NMR (CDCl3, ppm): 204.2, 164.6, 135.8, 134.9, 134.5, 132.6, 131.1, 129.8, 129.7, 128.8, 76.8, 66.9, 28.3.
97% With dmap; triethylamine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere; 18 Under nitrogen atmosphere 1.25 grams of benzene-1,3,5-tricarbonyl trichloride dissolved in 5 mL of dry dichloromethane was added dropwise to a pre-cooled 20 mL of dichloromethane solution at 0° C. containing 2.74 grams of 2-hydroxy-1-(3-(hydroxymethyl)phenyl)-2-methylpropan-1-one, 2 mL of Et3N and 50 mg of N,N-dimethylpyridin-4-amine. The mixture was stirred for 2 hrs and gradually warmed to room temperature. The mixture was concentrated and then diluted by 100 mL of ethyl acetate, washed successively by saturated NaHCO3 and brine of half volume. The organic layer was dried and concentrated, and the crude product was further purified by silica gel column chromatography with mixtures of hexane/ethyl acetate (V/V=2/1) to give the target product as colorless oil (97% yield). 1H NMR (CDCl3, ppm): 8.88 (s, 3H), 8.15 (s, 3H), 8.01 (d, 3H, J=7.8 Hz), 7.62 (d, 3H, J=7.5 Hz), 7.46 (dd, 3H, J=7.8 Hz, J=7.5 Hz), 5.43 (s, 6H), 4.02 (s, 3H), 1.59 (s, 18H); 13C NMR (CDCl3, ppm): 204.2, 164.6, 135.8, 134.9, 134.5, 132.6, 131.1, 129.8, 129.7, 128.8, 76.8, 66.9, 28.3.
  • 53
  • [ 4422-95-1 ]
  • [ 16091-26-2 ]
  • [ 1422521-33-2 ]
YieldReaction ConditionsOperation in experiment
In 1-methyl-pyrrolidin-2-one; at 45 - 90℃; for 1.25h; The synthesis of Compound D from trimesoyl chloride, benzoyl chloride and 1,3-phenylene diamine can be performed according to the following scheme: [0079] The experimental set up consisted of a 1 L glass beaker equipped with a glass rod stirrer coupled with an overhead mechanical stirrer. 1,3 phenylene diamine (20 g) was dissolved in warm dimethyl acetamide (200 mL) (alternatively N-methyl pyrrolidone can also be used) and maintained at 45 C. Next benzoyl chloride (26.51 g) was slowly added drop wise over a period of 1.5 to 2 hours, to the amine solution with constant stirring. The rate of addition of the benzoyl chloride was maintained such that the reaction temperature was maintained less than 60 C. After complete addition of the benzoyl chloride, the reaction mixture was gradually warmed to 85-90 C. and then allowed to cool to around 45-50 C. At this point, trimesoyl chloride (16.03 g) was gradually added to the reaction mixture such that the exotherm did not increase the reaction temperature above 60 C. After complete addition of the trimesoyl chloride, the reaction mixture was allowed to stir for additional 45 minutes, after which the reaction temperature was increased to 90 C. for about 30 minutes and then was cooled to room temperature. The mixture was allowed to rest overnight at room temperature. The product was recovered by precipitation through the addition of 1.5 L of distilled water, which was followed by was vacuum filtration using a filter paper and a Buchner funnel. The crude product was then washed with acetone (250 mL) and washed again with hot water (500 mL). The product (yield: ca. 90%) was then air dried over night at room temperature and then was dried in a vacuum oven 150 C. for 4 to 6 hours. The product was a pale tan solid. The Proton NMR characterization was as follows: 1H NMR (400 MHz d6-DMSO): 10.68 (s, 3H, CONH), 10.3 (s, 3H, CONH), 8.74 (s, 3H, central Ar), 8.1 (d, 3H, m-phenylene Ar), 7.9 (d, 6H, ortho-ArH), 7.51 (m, 15H, meta-para-ArH and 6H, m-phenylene Ar) and 7.36 (m, 3H, m-phenylene Ar).
  • 54
  • [ 4422-95-1 ]
  • [ 150-13-0 ]
  • 4,4',4"-((benzene-1,3,5-tricarbonyl)tris(azanediyl))tribenzoic acid [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With potassium carbonate In propan-2-one at 80℃; for 16h; Inert atmosphere; Reflux;
92% With potassium carbonate In propan-2-one for 16h; Reflux;
92% With potassium carbonate In propan-2-one Inert atmosphere; Reflux; 2 2. Synthesis of 4,4′,4″-((benzene-1,3,5-tricarbonyl)tris(azanediyl))tribenzoic acid (H3BTCB) This compound was synthesized according to the reported procedure. Under Ar atmosphere, 4-aminobenzoic acid (about 4.94 g, about 36 mmol) was dissolved in about 100 mL anhydrous acetone. Dry K2CO3 (about 4.54 g, about 33 mmol) was added in the solution. To this reaction, a solution of 1,3,5-benzenetricarbonyltrichloride (about 2.5 g, about 9 mmol) in about 5 mL of anhydrous acetone was added by dropwise. The suspension refluxed for about 16 h and a yellow solid formed. After filtration, the solid was washed with large amount of acetone and 1 M aqueous HCl solution to obtain about 5.0 g (about 9.0 mmol, about 92%) pure product. 1H NMR (500 MHz, DMSO-d6): δ(ppm)=7.96-8.04 (m, 12H), 8.79 (s, 3H), 11.0 (s, 3H).
86% With triethylamine In tetrahydrofuran at 20℃; for 16h; Inert atmosphere;
84% With potassium carbonate In propan-2-one at 79.84℃; for 12h; Inert atmosphere;
84% With potassium carbonate In propan-2-one at 80℃; for 20h; Inert atmosphere;
Ca. 35 mg With anhydrous sodium carbonate In tetrahydrofuran at 20℃; 81 PREPARATION EXAMPLE EX81 PREPARATION EXAMPLE EX81 (0402) This example demonstrates the production of benzene-1,3,5-tricarboxylic acid tris-(4-carboxybenzene)amide having the following structure (0403) (0404) In a three neck round bottom flask, 21.2 g of sodium carbonate and 100 mL of tetrahydrofuran were added. Then, 13.75 g of 4-aminobenzoic acid and 8 g of 1,3,5-benzenetricarbonyl trichloride were each separately diluted in 15 mL of THF and added into the reaction simultaneously via two addition funnels. The reaction was stirred overnight at room temperature. About 80 mL of tetrahydrofuran was added to compensate the evaporation during the reactions and an additional 10.6 gram of sodium carbonate was added. Three hours later, the reaction was transferred to a 1 L beaker with 600 mL of water. The pH was adjusted to about 2 with hydrochloric acid. The product precipitated out and was collected by filtration. The product was then partially dried in a vacuum oven at 40° C. About 35 gram of wet product was obtained
0.9% In 1-methyl-pyrrolidin-2-one at 0 - 20℃; for 24.5h; Inert atmosphere; 2.2. Synthesis of H3TCPBT, N, N', N''-tris(p-carboxyphenyl)-1,3,5-benzenetriamide N, N', N''-tris(p-carboxypheny1)-1,3,5-benzenetriamide, H3TCPBT, was synthesized by a modification of the reported procedure [13]. p-Aminobenzoic acid (2.40 g, 17.5 mmol)were dissolved in 80 mL anhydrous N-methyl-2-pyrrolidinone at 0 °C. Under N2 flow, trimesoylchloride (1.33 g, 5.0 mmol) was added in one portion. After stirring for 30 min at 0 °C and 24 h at room temperature, the reaction solution was poured into a large excess of methanol. The precipitated white solid was filtered and washed repeatedly with hot methanol. The solid was finally dried in a vacuum oven at 80 °C to obtain a white powder (2.55 g, 90% yield). Anal. Calcd for C30H21N3O9: C, 63.49; H, 3.73; N,7.40. Found: C, 63.41; H, 3.77; N, 7.47. 1H NMR (DMSO-d6, δ ppm, see Figure S1):12.793 (broad peak, 3H, COOH), 10.970 (s, 3H, CONH), 8.795 (s, 3H, ArH), 8.004 (q, 12H,ArH). IR (KBr, cm-1, see Figure S2): 2658, 1701, 1676, 1601, 1533, 1408, 1319, 1253,1177, 1117, 1017, 956, 916, 854, 770, 719, 503.
Stage #1: 4-amino-benzoic acid With potassium carbonate In propan-2-one at 20℃; for 0.25h; Inert atmosphere; Stage #2: 1,3,5-benzene tris(carbonyl chloride) In propan-2-one at 60℃; Inert atmosphere;
2 2. 2. Synthesis of 4,4',4"-((benzene-1,3,5-tricarbonyl)tris(azanediyl))tribenzoic acid (H3BTCB) This compound was synthesized according to the reported procedure. Under Ar atmosphere, 4-aminobenzoic acid (about 4.94 g, about 36 mmol) was dissolved in about 100 mL anhydrous acetone. Dry K2CO3 (about 4.54 g, about 33 mmol) was added in the solution. To this reaction, a solution of 1,3,5-benzenetricarbonyltrichloride (about 2.5 g, about 9 mmol) in about 5 mL of anhydrous acetone was added by dropwise. The suspension refluxed for about 16 h and a yellow solid formed. After filtration, the solid was washed with large amount of acetone and 1 M aqueous HCl solution to obtain about 5.0 g (about 9.0 mmol, about 92%) pure product. 1H NMR (500 MHz, DMSO-d6): δ(ppm)=7.96-8.04 (m, 12H), 8.79 (s, 3H), 11.0 (s, 3H).

Reference: [1]Kutzscher, Christel; Hoffmann, Herbert C.; Krause, Simon; Stoeck, Ulrich; Senkovska, Irena; Brunner, Eike; Kaskel, Stefan [Inorganic Chemistry, 2015, vol. 54, # 3, p. 1003 - 1009]
[2]Jiang, Hao; Jia, Jiangtao; Shkurenko, Aleksander; Chen, Zhijie; Adil, Karim; Belmabkhout, Youssef; Weselinski, Lukasz J.; Assen, Ayalew H.; Xue, Dong-Xu; O'Keeffe, Michael; Eddaoudi, Mohamed [Journal of the American Chemical Society, 2018, vol. 140, # 28, p. 8858 - 8867]
[3]Current Patent Assignee: KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGY - US2022/106334, 2022, A1 Location in patent: Paragraph 0369
[4]Howe, Richard C. T.; Smalley, Adam P.; Guttenplan, Alexander P. M.; Doggett, Matthew W. R.; Eddleston, Mark D.; Tan, Jin Chong; Lloyd, Gareth O. [Chemical Communications, 2013, vol. 49, # 39, p. 4268 - 4270]
[5]Gruenker, Ronny; Bon, Volodymyr; Mueller, Philipp; Stoeck, Ulrich; Krause, Simon; Mueller, Uwe; Senkovska, Irena; Kaskel, Stefan [Chemical Communications, 2014, vol. 50, # 26, p. 3450 - 3452]
[6]Abazari, Reza; Yazdani, Elnaz; Nadafan, Marzieh; Kirillov, Alexander M.; Gao, Junkuo; Slawin, Alexandra M. Z.; Carpenter-Warren, Cameron L. [Inorganic Chemistry, 2021, vol. 60, # 13, p. 9700 - 9708]
[7]Current Patent Assignee: MILLIKEN & COMPANY - US9200142, 2015, B2 Location in patent: Page/Page column 64
[8]Zeng, Wenjiang; Wang, Guanyu; Zheng, Baishu; Wang, Zhaoxu; Bai, Junfeng [Journal of Coordination Chemistry, 2021, vol. 74, # 1-3, p. 241 - 251]
[9]Qiao, Junyi; Zhang, Borong; Yu, Xueyue; Zou, Xiaoqin; Liu, Xinyao; Zhang, Lirong; Liu, Yunling [Inorganic Chemistry, 2022, vol. 61, # 8, p. 3708 - 3715]
[10]Current Patent Assignee: KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGY - US2022/106334, 2022, A1
  • 55
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  • [ 116668-47-4 ]
  • [ 1431933-38-8 ]
  • 56
  • [ 944-43-4 ]
  • [ 4422-95-1 ]
  • [ 1431933-39-9 ]
  • 57
  • [ 1430325-32-8 ]
  • [ 4422-95-1 ]
  • [ 1430325-25-9 ]
YieldReaction ConditionsOperation in experiment
90% With dmap In dichloromethane at 40℃; for 18h; 4.2.10 Hypercore 8 A mixture of benzyl alcohol 3b (2.4 g, 3.47 mmol), benzene-1,3,5-tricarbonyl chloride28 (265 mg, 1.00 mmol) and DMAP (423 mg, 3.47 mmol) in CH2Cl2 (50 mL) was heated at 40°C. After 18h the reaction mixture was cooled, filtered and evaporated under reduced pressure to give hypercore 8 (1.99 g, 90%) as a white solid, mp 93-94°C; Rf 0.41 (50% Et2O in hexane); νmax 2926, 2872, 1724, 1233, 1165, 814cm-1; δH (600 MHz, CDCl3) 8.90 (3H, s, 3× CH), 7.51 (12H, d, J 8.5, 12× CH), 6.65 (12H, d, J 8.5, 12× CH), 6.56 (6H, s, 6× CH), 6.40 (3H, s, 3× CH), 5.30 (6H, s, 3× CH2), 4.05-3.90 (24H, m, 12× OCH2) and 1.95-1.90 (24H, m, 12× CH2); δC (75 MHz, CDCl3) 164.7 (C, quat.), 160.3 (C, quat.), 158.8 (C, quat.), 138.1 (CH), 137.5 (C, quat.), 134.9 (CH), 131.2 (C, quat.), 116.8 (CH), 106.7 (CH), 101.2 (CH), 82.6 (C, quat.), 67.5 (OCH2, two overlapping carbons), 67.3 (OCH2), 25.9 (CH2) and 25.8 (CH2). MALDI mass spectrum: calcd [M+Na]+ for C90H90I6 NaO18: 2243.029. Found: 2243.150.
  • 58
  • [ 4422-95-1 ]
  • 2,2',2"-(benzene-1,3,5-triyl)tris[1-phenyl-1H-benzimidazole] [ No CAS ]
YieldReaction ConditionsOperation in experiment
82.5% With N-phenyl-1,2-benzenediamine In 1-methyl-pyrrolidin-2-one at 80 - 195℃; for 7h; 8 Example 8 Synthesis of 1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene (BZZ-13) [TPBI] Example 8 Synthesis of 1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene (BZZ-13) [TPBI] [0030] Benzene-tricarbonyl trichloride (7.4 g, 0.028 mol.) was slowly added to 50 mL of anhydrous N-Methylpyrrolidinone (NMP) containing 19.5 g (0.106 mol.) of N-phenyl-o-phenylenediamine under moisture protection. Then the reaction mixture was heated from room temperature to 80° C. under stirring for 1 hour and then raises the reaction temperature to 180° C.-195° C. for 6 hours. After the reaction mixture was cooled to room temperature, 200 mL of water was added to reaction mixture with vigorously stirring. Then resulted precipitates were filtered and washed with water, mixture of water/alcohol. The pure product of 1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene (BZZ-13) [TPBI] (15.1 g) was obtained at yield of 82.5% by finally washed with acetone and dried.
  • 59
  • [ 71637-34-8 ]
  • [ 4422-95-1 ]
  • tris(3-thiophenylmethyl)trimesic ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With triethylamine In chloroform at 60℃; for 24h; Synthesis of Tris(3-thiophenylmethyl)trimersic Ester (L1). Triethylamine (16.5 mmol, 2.32 mL) was added to a stirred mixture of 1,3,5-benzenetricarbonyl trichloride (5mmol, 1.38 g) and 3-thiophenemethanol (15.8 mmol, 1.52mL) in chloroform (120 mL) at 60 °C. The reaction mixture was refluxed for 24 h. The solution was filtered, and added methanol (300 mL). Colorless crystals of L1 were obtained in 2 days in an 80 % yield.
  • 60
  • [ 4422-95-1 ]
  • [ 6937-16-2 ]
  • [ 1418125-76-4 ]
YieldReaction ConditionsOperation in experiment
79% With triethylamine; In tetrahydrofuran; at 0 - 20℃; Triethyl 4,4?,4?-[benzene-1,3,5-triyltris(carbonylimino)]tributanoate (7). To a solution of ethyl 4-aminobutyrate hydrochloride (1.983 g, 11.3 mmol) in THF (40 ml), a mixture of 1,3,5-benzenetricarbonyl trichloride (1.0 g, 3.8 mmol) and triethylamine (3.5 ml, 25 mmol) was added dropwise at 0 C. The reaction mixture was stirred at r. t. overnight, then poured into water (120 ml), extracted with Et2O (4×40 ml) and dried over Na2SO4. The solvent was evaporated, and the product was purified by column chromatography (SiO2, CH2Cl2/EtOAc/MeOH, 45:45:10) to give the title compound as a white solid. Yield: 1.65 g, 79%. MALDI-TOF (m/z): calc. for C27H39N3O9: 549.6, found 550.5 [M+H]+, 572.5 [M+Na]+, 588.5 [M+K]+. NMR 1H (DMSO-d6), epsilon, ppm: 1.16 (9H, t, 3J=7.0, Hz, -OCH2CH3), 1.79 (6H, dddd, 3J1=3J2=3J3=3J4=7.3 Hz, -CH2-), 2.35 (6H, t, 3 J=7.3 Hz, -CH2C(O)-), 3.27-3.33 (6H, m, broad, -NHCH2-), 4.04 (6H, q, 3J=7.0 Hz, -OCH2CH3), 8.37 (3H, s, Ar), 8.71 (3H, t, 3J=5.5 Hz, -NH-).
  • 61
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  • [ 92352-29-9 ]
  • [ 1610948-36-1 ]
YieldReaction ConditionsOperation in experiment
52% In acetonitrile Reflux;
  • 62
  • [ 602-88-0 ]
  • [ 4422-95-1 ]
  • [ 100953-52-4 ]
  • [ 1149597-92-1 ]
YieldReaction ConditionsOperation in experiment
In 1-methyl-pyrrolidin-2-one; water 1 Synthesis of 1,3,5-tris[1-(4-bromophenyl)-1H-benzo[d]imidazol-2-yl]benzene (Compound 1) Example 1 Synthesis of 1,3,5-tris[1-(4-bromophenyl)-1H-benzo[d]imidazol-2-yl]benzene (Compound 1) N-(4-bromophenyl)-1,2-phenylenediamine (1.64 g, 6.23 mmol) was dissolved in 1-methyl-2-pyrrolidinone (NMP) (7 mL). To the solution 1,3,5-benzenetricarbonyl trichloride (0.551 g, 2.08 mmol) was added portion-wise under nitrogen. The reaction mixture was stirred at room temperature for 2 h, and then the reaction temperature was raised to 50° C. for additional 30 min. After cooling the reaction mixture was poured into cold water (50 mL). The resulting precipitates were filtered off and washed with water to give crude tribenzamide. The tribenzamide was heated at 250° C. for 3 h under nitrogen. After cooling water (50 mL) was added to the mixture, and extracted with CH2Cl2 (50*3 mL). The combined organic layers were washed with water and brine, and then dried over Na2SO4. Solvent of the filtrate was removed in vacuo to obtain a crude solid. 1,3,5-Tris[1-(4-bromophenyl)-1Hbenzo[d]imidazol-2-yl]benzene was isolated by silica gel column chromatography (solvent: EtOAc) (1.63 g, 88%). 1H NMR (300 MHz, CDCl3, 8): 7.87 (s, 3H), 7.85 (d, J=7.5 Hz, 3H), 7.60 (d, J=8.7 Hz, 6H), 7.27-7.39 (m, 6H), 7.18 (d, J=7.4 Hz, 3H), 7.06 (d, J=8.7 Hz, 6H); 13C APT NMR (75.5 MHz, CDCl3, 8): 150.6 (C), 143.2 (C), 137.3 (C), 135.8 (C), 133.6 (CH), 131.3 (CH), 131.1 (C), 129.1 (CH), 124.3 (CH), 123.8 (CH), 123.0 (C), 120.6 (CH), 110.6 (CH); MALDI-TOF-MS (m/z): 893 [M+H+]; Anal. calcd for C45H27Br3N6: C, 60.63; H, 3.05; N, 9.43. Found: C, 60.71; H, 2.93; N, 9.47.
  • 63
  • [ 4422-95-1 ]
  • [ 14358-33-9 ]
  • (1R,3R,5RS)-1,3,5-benzenetricarbonyl tri-(R-(D)-aspartic dimethyl ester) [ No CAS ]
  • 64
  • C18H19NO2 [ No CAS ]
  • [ 4422-95-1 ]
  • C63H57N3O9 [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With triethylamine In chloroform at 20℃; for 2h; 8.5 Step 5: Synthesis of trifunctional nitrileoxide 11 OH diphenyl nitrileoxide 5 (0.43 g, 1.5 mmol) was dissolved in chloroform (10 mL), and triethylamine (0.43 mL, 3.1 mmol) was added. The solution was cooled to 0° C., and a solution in which trimesoyl chloride (0.12 g, 0.45 mmol) was dissolved in chloroform (5 mL) was added. The temperature was returned to a room temperature, and the mixture was stirred for 2 hours. The mixture was washed with water 2 times and brine 1 time, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a pale yellow solid (0.43 g, 4.3 mmol, 96%). 1H-NMR spectrum and IR spectrum are shown in FIG. 6 and FIG. 7, respectively. (0480) 1H NMR (400 MHz, 298 K, CDCl3): δ 9.20 (s, 3H), 7.40-7.25 (m, 27H), 2.40 (t, J=6.9 Hz, 6H), 1.38 (m, 12H), 0.90-0.89 (t, J=6.9 Hz, 9H) ppm
  • 65
  • [ 4422-95-1 ]
  • [ 22483-09-6 ]
  • 1,3,5-tris(2,2-dimethoxyethylaminocarbonyl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
98% With N-ethyl-N,N-diisopropylamine In chloroform at 20℃; for 24h; Preparation of compound 1d. At -15 °C, in an anhyd. CHCl3 (50 mL) and well stirred solution containing DMEA (2.68 mL, 2.61 g, 24.86 mmol) and DIPEA (diisopropylethylamine, 4.23 mL, 3.21 g, 24.86 mmol), an anhyd. CHCl3 (5 mL) solution containing trimesic acid trichloride (2.00 g, 7.52 mmol) was injected dropwise. The resulting solution was let to reach gently the room temperature and kept, with stirring, for additional 24 h. After this period, TLC monitoring (eluent acetone : ligroin 1:1 v/v, visualization in UV at λ=254 nm) indicated formation of the product as a single spot. The reaction mixture was evaporated in vacuum to dryness to provide an yellow oil. Cooled water (20 mL) was added and the resulted suspension was stirred at room temperature for 2 h to the complete extraction of DIPEA hydrochloride. The suspension was then cooled at 0 - 5 °C overnight then filtered off and well washed with cooled water to give 3.48 g pure compound 1d (98% yield with respect to trimesic acid trichloride).
98% With N-ethyl-N,N-diisopropylamine In chloroform at -15 - 20℃; for 24h;
  • 66
  • [ 462-06-6 ]
  • [ 4422-95-1 ]
  • [ 267668-44-0 ]
YieldReaction ConditionsOperation in experiment
92.7% With aluminum (III) chloride; at 85 - 97℃; for 2h; Fluorobenzene 100 parts by weight a molecular sieve (Molecular sieve 3A beads 4-8 mesh, aldrich) have a water 0.1 parts by weight was filtering after time 1. Bead type in 30 nm pore size from said molecular sieve has (pore size) was employed. Furthermore, fluorobenzene filtered to reacted at ambient 248.86 g are input, in an aluminum chloride (AlCl3) 74.67 g 200 rpm was turned on is set in agitating section. After this filtered fluorobenzene 35.55 g and of 42.28 g chloride tree tree carbonyl benzene 1, 3, 5-10 minutes the solution was blended input. After completion blended with internal temperature 85 C or more reflux is 97 C temperature external connection is set up between the temperature inside an item to be heated to elevated temperature section. From the view point to the Reflux 2 after a time the cooled down to the normal temperature. Thus-obtained reaction solution at a blended for (ethanol) 568.8 g ethanol yields particles. After crystallization dope the n bit parallel data inputted filtration, 142.2 g ethanol at 5 times the tube. A particle produced 80 C the vacuum drying in a destination blanker obtained. Blanker been to obtain wife 65.93 g, yield is 92.7%, the purity of 99.96% (HPLC Area %) power is fed, was white color
  • 67
  • [ 1256087-71-4 ]
  • [ 4422-95-1 ]
  • C105H84N6O9 [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% With triethylamine In tetrahydrofuran at 20℃; for 48h; Inert atmosphere; 2.2. Synthesis and characterization of compound 3 A solution of N1,N1-bis(4-(benzyloxy)phenyl)benzene-1,4-diamine7 (356 mg, 754 mmol) and 1,3,5-benzenetricarbonyl trichloride (57 mg, 215 mmol) in dryTHF (2 mL) was treated with triethylamine (150 mL,1.08 mmol). The resulting solutionwas then stirred at roomtemperature for two days under argon. After removal of thesolvents, the crude product was purified by column chromatography(SiO2, toluene / EtOAc/toluene: 5/95). Thesolid was then washed with cyclohexane and diethyl ether,and further triturated with diethyl ether to yield compound3 (281 mg, 83%) as a yellow solid. Rf 0.77 (50/50 EtOAc/cyclohexane); 1H NMR (400 MHz, CDCl3, 298 K): d 8.42(brs, 3H), 8.38 (brs, 3H), 7.41e7.28 (m, 36H), 6.97 (d,3J 9.0 Hz, 12H), 6.87 (d, 3J 11.2 Hz, 6H), 6.84 (d,3J 9.0 Hz, 12H), 4.97 (s, 12H); 1H NMR (400 MHz, C7D8/CD3OD(5%), 298 K): d 8.63 (s, 3H), 7.74 (d, 3J 8.9 Hz, 6H),7.24 (d, 3J 7.3 Hz, 12H), 7.14 (t, 3J 7.3 Hz, 12H), 7.07 (s,6H), 7.06 (d, 3J 9.0 Hz, 6H), 7.01 (d, 3J 8.8 Hz, 12H), 6.77(d, 3J 8.8 Hz,12H), 4.70 (s,12H); 13C NMR (100 MHz, C7D8/CD3OD(5%), 298 K): d 165.88, 155.64, 146.39, 142.06,137.91,136.42,132.47,129.76,129.28,128.78,128.36,128.09,127.77, 126.58, 122.61, 122.32, 116.25, 70.49; FT-IR (ATR):y 3418, 3278, 3036, 2923, 2860, 1678, 1651, 1634, 1599,1499, 1453, 1310, 1236, 1221, 1162, 1025, 826 cm1; ESI-MS:m/z calcd for C105H84N6O9: 1572.63 [M], found 1572.66.
  • 68
  • [ 4422-95-1 ]
  • [ 35453-19-1 ]
  • C33H12I9N3O15 [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% With dmap; In N,N-dimethyl acetamide; at 25℃; for 12h;Inert atmosphere; In a reactor equipped with a stirrer and a nitrogen inlet tube, Under a nitrogen atmosphere <strong>[35453-19-1]5-amino-2,4,6-triiodoisophthalic acid</strong> (230 parts), N, N-dimethyl-4-aminopyridine (DMAP) (5 parts) and N, N- dimethylacetamide (DMAc) (400 parts) were added Followed by stirring. Thereafter, slowly 1,3,5-benzenetricarbonyl trichloride (30 parts) was added, and the reaction was carried out for 12 hours while maintaining the reaction temperature at 25 C. After completion of the reaction, the reaction solution was poured into pure water (1800 parts), the precipitate was separated by filtration and vacuum dried at 50 C. to obtain 150 parts (71%) of intermediate product 2.
  • 69
  • [ 4422-95-1 ]
  • C13H16N4O2 [ No CAS ]
  • C48H42N12O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With <i>N</i>,<i>N</i>-dimethyl-aniline In 1-methyl-pyrrolidin-2-one; toluene at 20℃; for 2h; Cooling with ice; 2 Synthesis of Compound (2) To NMP (50 mL), 8.9 g of the amidoxime derivative and N,N-dimethyl aniline (5.2 mL) were added, then added dropwise with NMP solution (10 mL) of trimesic acid chloride (2.6 g) while being cooled with ices, and was stirred for two hours at the room temperature. The mixture was added with toluene (50 mL), and was dehydrated by azeotropy for three hours. After toluene was distilled away, the resultant was poured into dilute hydrochloric acid, was filtered, was washed with water, then was dried, and then was purified according to a column chromatography to give 8 g (88% yield constant) of a target compound, Compound (2). The identification of the compound was carried out by 1H-NMR. 1H-NMR (CDCl3) δ:1.01 (9H, t), 1.431.60 (6H, m), 1.851.98 (6H, m), 3.05 (6H, t), 7.70 (3H, t), 8.30 (3H, d), 8.45 (3H, d), 8.95 (3H, s), 9.28 (3H, s). The phase transition temperature of the obtained Compound (2) was studied by texture observation of the compound with polarization microscope. Raising the temperature to around 201 degrees Celsius, the phase was changed from the crystal phase to the discotic nematic phase; and further raising the temperature to more than 268 degrees Celsius, the phase was changed to the isotropic liquid phase. That is, from these results, it can be understood that Compound (2) exhibits a discotic nematic phase at a temperature within the range from 210 to 268 degrees Celsius.
  • 70
  • [ 4422-95-1 ]
  • [ 38017-65-1 ]
  • C66H66N6O12 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: methyl L-phenylalanyl-L-phenylalaninate hydrochloride salt With triethylamine In dichloromethane for 0.166667h; Stage #2: 1,3,5-benzene tris(carbonyl chloride) In dichloromethane for 24h;
  • 71
  • [ 4422-95-1 ]
  • 1-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazine [ No CAS ]
  • [3,5-bis[4-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazine-1-carbonyl]phenyl]-[4-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazin-1-yl]methanone [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With triethylamine In dichloromethane at 20℃; for 16h; Inert atmosphere; 10 Preparative Example 10 (PE10) l-(l, l,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazine (146 g, 396.5 mmol, 3.01 equiv.), triethylamine (61 mL, 438 mmol, 3.3 equiv.) and dichloromethane (300 mL, 4680 mmol) were added to a 3 -neck 3 L round bottom equipped with a mechanical stirrer, addition funnel and a claisen adaptor with thermocouple, reflux condenser and addition funnel containing benzene- 1,3, 5 -tricarbonyl chloride (35 g, 131.84 mmol) under nitrogen atmosphere. Benzene- 1,3, 5 -tricarbonyl chloride was slowly added via addition funnel to the reaction mixture with vigorous stirring. Upon completion, the mixture was allowed to stir for 16 h at r.t.. Water (300 mL) was then added to the white suspension and the product was collected via filtration. The solid was washed 3x with water (300 mL) and 3x with dichloromethane (300 mL) and dried under vacuum to afford [3,5-bis[4- (1, 1,2,2,3, 3, 4,4,4-nonafluorobutylsulfonyl)piperazine-l-carbonyl]phenyl]-[4- (l,l,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)piperazin-l-yl]methanone (159.7 g, 126.7 mmol, 96% Yield) as a white solid. The identity of the material was confirmed by LC/MS and NMR techniques.
  • 72
  • [ 4422-95-1 ]
  • [ 123-08-0 ]
  • C30H18O9 [ No CAS ]
YieldReaction ConditionsOperation in experiment
98% With triethylamine In tetrahydrofuran at 10 - 20℃; for 2h; 37 Synthesis Example 37 Synthesis of compound represented by formula [78] (4- (2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene) methyl) phenyl] propionate benzene-1,3,5-tricarbonate 4-hydroxybenzaldehyde [76] (35.7 g, 292 mmol), triethylamine (31.5 g, 311 mmol) and tetrahydrofuran (150 g) were added to a 1 L four-necked flask and the inner temperature was cooled to 10 ° C. (25.0 g, 94 mmol) in tetrahydrofuran (2258) was added dropwise, and the reaction was terminated at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into pure water (2250 g), and the precipitated solid was collected by filtration.And the residue was dried to give 48.0 g of the compound [77] (yield 98%).
  • 73
  • [ 4422-95-1 ]
  • [ 214360-73-3 ]
  • N<SUP>1</SUP>,N<SUP>3</SUP>,N<SUP>5</SUP>-tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzene-1,3,5-tricarboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% With triethylamine In dichloromethane at 4 - 20℃; for 18h; N1,N3,N5-tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzene-1,3,5-tricarboxamide (3a) After cooling a solution of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (1a) (657.3 mg, 3.00 mmol) and CH2Cl2 (4.348 mL) at 4.0C with stirring under atmospheric conditions, Et3N (623.8 mL, 4.50 mmol) and 1,3,5-benzenetricarbonyl chloride (2)(265.5 mg, 1.00 mmol) were added. The resulting solution was stirred for 18 h at room temperature and then water (ca. 100 mL) was added. The mixture was extracted with AcOEt (x3) and the combined organic extract was dried over anhydrous Na2SO4. After filtration, the solvents were evaporated under reduced pressure. The obtained crude material was washed with AcOEt/n-hexane to give the desired product (3a) (743.3 mg, 91%yield) as a white solid. Mp >250C; IR (KBr) 3450 (NH), 1648 cm1 (C D O); FAB-MS(positive) m/z 814 (MCH)C. HRMS (FAB) Calcd for C45H55B3N3O9C: m/z 814.4212(MCH)C. Found: 814.4209; 1H-NMR (DMSO-d6) d 1.30 (36H, s, CH3), 7.70 (6H, d, J D8.4 Hz, Ar H-3, H-5 in B-C6H4-N), 7.88 (6H, d, J D 8.4 Hz, Ar H-2, H-6 in B-C6H4-N),8.72 {3H, s, Ar H-2, H-4, H-6 in C6H3-[C( D O)]3}, 10.73 (3H, s, NH); 13C-NMR(DMSO-d6) d 24.7 (CH3), 83.5 (B-O-C-C-O-B), 119.3 (Ar C-2, C-6 in B-C6H4-N), 130.0{Ar C-2 in C6H3-[C( D O)]3}, 135.2 (Ar C-3, C-5 in B-C6H4-N), 135.3 {Ar C-1 in C6H3-[C( D O)]3}, 141.8 (Ar C-1 in B-C6H4-N), 164.6 (C D O).Anal. Calcd. for C45H54B3N3O9.H2O: C, 65.01; H, 6.79; N, 5.05. Found: C, 65.02; H,6.67; N, 5.25.
  • 74
  • [ 4422-95-1 ]
  • [ 210907-84-9 ]
  • N<SUP>1</SUP>,N<SUP>3</SUP>,N<SUP>5</SUP>-tris(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzene-1,3,5-tricarboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With triethylamine In dichloromethane at 4 - 20℃; for 18h; N1,N3,N5-tris(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzene-1,3,5-tricarboxamide (3b) After cooling a solution of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (1b)(657.3 mg, 3.00 mmol) and CH2Cl2 (4.348 mL) at 4.0C with stirring under atmospheric conditions, Et3N (623.8 mL, 4.50 mmol) and 1,3,5-benzenetricarbonyl chloride (2)(265.5 mg, 1.00 mmol) were added. The resulting mixture was stirred at room temperaturefor 18 h and then water (ca. 100 mL) was added. The mixture was extracted with AcOEt (x3) and the combined organic extract was dried over anhydrous Na2SO4. After filtration, the solvents were evaporated under reduced pressure. The obtained crude material was washed with AcOEt/n-hexane to give the desired product (3b) (659.3 mg, 81% yield) as a white solid. Mp 183-191C; IR (KBr) 3465 (NH), 1653 cm1 (C D O); FABMS(positive) m/z 814 (MCH)C. HRMS (FAB) Calcd for C45H55B3N3O9C: m/z 814.4212(MCH)C. Found: 814.4209; 1H-NMR (DMSO-d6) d 1.32 (36H, s, CH3), 7.38-7.48 (6H,m, Ar H-4, H-5 in B-C6H4-N), 8.06-8.11 (3H, m, Ar H-6 in B-C6H4-N), 8.12 (3H, s, ArH-2 in B-C6H4-N), 8.78{3H, s, Ar H-2, H-4, H-6 in C6H3-[C( D O)]3}, 10.58 (3H, s,NH); 13C-NMR (DMSO-d6) d 24.7 (CH3), 83.7 (B-O-C-C-O-B), 123.2 (Ar C-6 inB-C6H4-N), 126.4 (Ar C-2, in B-C6H4-N), 128.4 (Ar C-5 in B-C6H4-N), 129.8 (Ar C-4 inB-C6H4-N), 129.8 {Ar C-2 in C6H3-[C( D O)]3}, 135.2 {Ar C-1 in C6H3-[C( D O)]3},138.6 (Ar C-1 in B-C6H4-N), 164.3 (C D O).Anal. Calcd. for C45H54B3N3O9.H2O: C, 65.01; H, 6.79; N, 5.05. Found: C, 64.87;H, 6.80; N, 5.15.
  • 75
  • [ 931-40-8 ]
  • [ 4422-95-1 ]
  • benzene-1,3,5-tricarboxylic acid tris-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
75.1% With triethylamine In acetone at 20℃; for 12h; Cooling with ice; Inert atmosphere; 2.1 Synthesis of benzene-1,3,5-tricarboxylic acid tris-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester (BATE1) In a dry 250 mL 3-necked round-bottomed glass flask equipped with a magnetic stirrer, a funnel with pressure-equalising tube and a thermometer was placed 4.13 g (0.035 mol) of glycerol carbonate, 4.16 mL (0.03 mol) of triethylamine and 60 mL of anhydrous acetone as solvent. A solution of trimesoyl chloride (2.65 g, 0.01 mol) in anhydrous acetone (40 mL) was added dropwise to the above solution cooled in ice bath under nitrogen atmosphere. The mixture was stirred at room temperature for 12 h. After reaction, triethylamine hydrochloride was removed by filtration. Then, the filtrate was evaporated under reduced pressure; the obtained residue was washed by deionized water for several times to give the product (3.83 g, yield 75.10%) (reaction 2, Scheme 1 ). 1H NMR (400 MHz, DMSO-d6): δ 8.68 (s, 3H), 5.29-5.18 (m, 3H), 4.82-4.41 (m, 12H) (Fig. S1). FTIR (νmax cm-1): 2923, 1794, 1734, 1245, 1050, 738.
  • 76
  • [ 5159-59-1 ]
  • [ 4422-95-1 ]
  • C45H33N3O9 [ No CAS ]
  • 77
  • [ 108-86-1 ]
  • [ 4422-95-1 ]
  • benzene-1,3,5-triyltris((4-bromophenyl)methadone) [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With aluminum (III) chloride at 20 - 90℃; for 14h; Inert atmosphere; 2.2.1. Synthesis of benzene-1,3,5-triyltris((4-bromophenyl)methadone)(TBP-Br) Benzene-1,3,5-tricarbonyl trichloride (10 mmol, 2.65 g) and bromobenzene(80 mmol, 12.56 g) were added into a 50 mL two-neckedflask in N2 atmosphere, then stirred the mixture for 15 min.Subsequently, aluminum chloride (8 mmol, 1.07 g) was slowly addedinto the system. The mixtures were stirred for 12 h at room temperature,and then the temperature was slowly increased to 90 °C and keptfor 2 h. After the cooled down to room temperature, the reaction waspoured directly into deionized water and washed with deionized water5 to 6 times to remove residual HCl. The product was isolated by silicagel column chromatography using petroleum/dichloromethane=1:1as eluent to afford a white solid (5.67 g, 90% yield). 1H NMR (400 MHz,DMSO-d6) δ 8.25 (s, 3H), 7.85-7.77 (m, 12H). MS (EI) m/z:(M+):C27H15Br3O3, calculated: 627.13; measured: 627.30.
90% With aluminum (III) chloride at 20 - 90℃; for 2.5h; 1.1 Example 1. Synthesis of Compound (2-2) To a 500 mL two-necked flask 1,3,5-benzenetricarbonyl trichloride (26.5 g, 100 mmol) and bromobenzene (62.8 g, 400 mmol) were added and anhydrous aluminium chloride (66.5 g, 500 mmol) was added in batches t under stirring. After addition, the reaction solution was stirred and reacted at room temperature for 0.5 hours, heated at 90° C. for two hours before the end of reaction. The reaction product was slowly added to a hydrochloride aqueous solution, and suction-filtered, and the residue was recrystallized from a mixed solution of dichloromethane/ethanol, with a yield rate of 90%.
  • 78
  • [ 771-61-9 ]
  • [ 4422-95-1 ]
  • [ 247048-22-2 ]
YieldReaction ConditionsOperation in experiment
91% With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 4.5h; Inert atmosphere; Cooling with ice;
80% With dmap; N-ethyl-N,N-diisopropylamine In dichloromethane at 0℃; Synthesis of S5. Dimethylaminopyridine (DMAP, 10 mg), diisopropylethylamine (4.5 mL, 25.75 mmol) and pentafluorophenol (Pfp-OH, 1.58 g, 8.58 mmol) were dissolved in DCM (30 mL), stirring and keeping this mixture at 0 °C for 30 min. Then 1,3,5-benzenetricarbonyl trichloride (TMA, 0.50 g, 2.38 mmol) was added into the mixture, reacting overnight. When this reaction completed, the mixture was condensed and purified by column chromatography (DCM) to obtain S5 (2.05 g, 80%).
  • 79
  • [ 4422-95-1 ]
  • [ 57233-86-0 ]
  • N<SUP>1</SUP>,N<SUP>3</SUP>,N<SUP>5</SUP>-tris((R)-1-(4-nitrophenyl)ethyl)benzene-1,3,5-tricarboxamide [ No CAS ]
  • 80
  • [ 769-39-1 ]
  • [ 4422-95-1 ]
  • tris(2,3,5,6-tetrafluorophenyl) benzene-1,3,5-tricarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% With N-ethyl-N,N-diisopropylamine; In dichloromethane; at 0 - 20℃; for 4.16667h;Inert atmosphere; Under argon atmosphere, DIPEA (13.9 mL, 80 mmol, 4.0 eq.) and 2,3,5,6-<strong>[769-39-1]tetrafluorophenol</strong> (10.3 g, 60.4 mmol, 3.0 eq.) were dissolved in dry DCM (100 mL) and were subsequently added dropwise over 2.5 h to a rigorously stirred solution of benzene- 1, 3, 5-tricarbonyl trichloride (3.57 mL, 20.0 mmol, 1.0 eq.) in dry DCM (150 mL) at 0 C. After addition, the mixture was stirred for 40 min and was allowed to warm to 6 C, after which it was gradually heated to the ambient temperature and stirred for another 1 h. Then, the reaction mixture was washed with 1 M HC1 (320 mL) and with 1 M NaOH (320 mL). The alkaline aqueous layer was extracted with DCM (50 mL) and the combined organic layers were washed with brine (100 mL). The organic phase was dried with Na2S04, filtered, and evaporated under reduced pressure. After removal of solvents, a pale brown solid (12.1 g, 93% yield) was obtained. NMR (400 MHz, CDCb): d 9.30 (s, 3 H), 7.17-7.05 (m, 3 H)
93% Under argon atmosphere, DIPEA (13.9 mL, 80 mmol, 4.0 eq.) and 2,3,5,6-<strong>[769-39-1]tetrafluorophenol</strong> (10.3 g, 60.4 mmol, 3.0 eq.) were dissolved in dry DCM (100 mL) and were subsequently added dropwise over 2.5 h to a rigorously stirred solution of benzene-l, 3, 5-tricarbonyl trichloride (3.57 mL, 20.0 mmol, 1.0 eq.) in dry DCM (150 mL) at 0 C. After addition, the mixture was stirred for 40 min and was allowed to warm to 6 C, after which it was gradually heated to the ambient temperature and stirred for another 1 h. Then, the reaction mixture was washed with 1 M HC1 (320 mL) and with 1 M NaOH (320 mL). The alkaline aqueous layer was extracted with DCM (50 mL) and the combined organic layers were washed with brine (100 mL). The organic phase was dried with Na2S04, filtered, and evaporated under reduced pressure. After removal of solvents, a pale brown solid (12.1 g, 93% yield) was obtained. NMR (400 MHz, CDCL): d 9.30 (s, 3 H), 7.17-7.05 (m, 3 H)
  • 81
  • [ 67107-87-3 ]
  • [ 4422-95-1 ]
  • C45H81N3O6 [ No CAS ]
  • 82
  • [ 4422-95-1 ]
  • [ 1225387-53-0 ]
  • C18H15N9O3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
75.3% Stage #1: 1,3,5-benzene tris(carbonyl chloride); 3(5)-aminopyrazole In acetonitrile for 12h; Inert atmosphere; Reflux; Stage #2: With triethylamine In methanol at 20℃; for 3.5h; 3 Under nitrogen protection, dissolve trimesic acid chloride(10 mmol) and 5-aminopyrazole (30 mmol) in anhydrous acetonitrile (60 mL), stir and reflux for 12 hours, and filter with suction.The filter cake was dissolved in methanol, an excess of triethylamine was added to it, and the mixture was stirred at room temperature for 3.5 hours. A solid precipitated out, filtered, washed with cold water, and dried to obtain compound II-1 with a yield of 75.3%.
  • 83
  • [ 2577-90-4 ]
  • [ 4422-95-1 ]
  • [ 1567396-37-5 ]
YieldReaction ConditionsOperation in experiment
86% With triethylamine In dichloromethane at 0 - 60℃; for 13h; 1.3 (3) Dissolve L-phenylalanine methyl ester (5.91g, 33mmol) in dichloromethane (80mL) and slowly add it to Et3N (6.3ml, 45mmol) at 0°C, and then add it to the mixture Continue to slowly add 1,3,5-benzenetricarboxylic acid chloride (2.66g, 10mmol), the entire feeding process lasts for about 1 hour, and the above reaction mixture continues to be stirred and reacted for 12 hours at a temperature of 60°C. The reaction mixture was concentrated under reduced pressure and poured into 100 mL of water. The organic phase was extracted with ethyl acetate. The organic phase was washed with 2M HCl and saturated NaHCO3 solution. The organic phase was dried with Na2SO4, and then concentrated under reduced pressure to obtain 6.0 g of light yellow esterified compound. The product L-Me3, the yield is about 86%.
86% With triethylamine In dichloromethane at 0 - 60℃; for 13h;
  • 84
  • [ 4422-95-1 ]
  • [ 75-31-0 ]
  • [ 436149-16-5 ]
YieldReaction ConditionsOperation in experiment
78% With triethylamine In dichloromethane at 20℃; Cooling with ice; 2.1 General method for synthesis of bis and tris amides General procedure: According to a modified literature method [SI3] the primary amine (11.0 mmol, 1.10 equiv. (16c, 16d, 16e) or 22.0 mmol, 2.20 equiv. (16a) or 33.0 mmol, 3.30 equiv. (16b)) and triethylamine (25.0 mmol,2.50 equiv. (16a, 16c, 16d, 16e) or 37.5 mmol, 3.75 equiv. (16b)) were dissolved in DCM (approx.50 mL). The reaction mixture was cooled in an ice/water bath and the acyl chloride (20.0 mmol, 2.00 equiv. (16c, 16d, 16e) or 10.0 mmol, 1.00 equiv. (16a and 16b)) was added dropwise via syringe under vigorous stirring. During the addition, a white precipitate was formed. After addition was completed, the reaction mixture was warmed to room temperature and stirred for 30 minutes. The volatiles were removed under reduced pressure, aqueous HCl (1 M) was added, and the mixture was filtered. The residue was washed with aqueous HCl (1 M), water and ethyl acetate. If necessary, purification was accomplished by recrystallization (water/methanol 7:3).
  • 85
  • [ 16245-79-7 ]
  • [ 4422-95-1 ]
  • N1,N3,N5-tris(4-octylphenyl)benzene-1,3,5-tricarboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With triethylamine In tetrahydrofuran at 0 - 20℃; for 18h; Inert atmosphere;
Same Skeleton Products
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